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71.
Multidimensional potential energy landscapes (PELs) have a Gaussian distribution for the energies of the minima, but at the same time the distribution of the hyperareas for the basins of attraction surrounding the minima follows a power-law. To explore how both these features can simultaneously be true, we introduce an “egg-box” model. In these model landscapes, the Gaussian energy distribution is used as a starting point and we examine whether a power-law basin area distribution can arise as a natural consequence through the swallowing up of higher-energy minima by larger low-energy basins when the variance of this Gaussian is increased sufficiently. Although the basin area distribution is substantially broadened by this process, it is insufficient to generate power-laws, highlighting the role played by the inhomogeneous distribution of basins in configuration space for actual PELs. 相似文献
72.
Guillaume Lafitte Audrey Beillard Sandrine Chambon Catherine Soulet Laurence Dumais Grégoire Mouis Jean-François Fournier Laurence Clary Claire Bouix-Peter Loic Tomas Craig S. Harris 《Tetrahedron letters》2018,59(3):256-259
During our search for novel CGRP antagonists, we had great difficulty in accessing one of our key motifs. Herein, we communicate how we solved the problem by an unprecedented Mitsunobu alkylation using unprotected amino alcohols. 相似文献
73.
Mark D. Tarn Damien Robert Claire Wilhelm 《Journal of magnetism and magnetic materials》2009,321(24):4115-4122
Free-flow magnetophoresis is becoming a popular technique for the separation and manipulation of magnetic particles and materials in microsystems. A wide variety of magnetic particles are commercially available that differ greatly in size and in magnetic properties. To investigate the suitability of different particle types for magnetophoretic operations in microfluidic devices, we compared a range of particles from three manufacturers by pumping them through a microfluidic separation chamber and deflecting them from the direction of laminar flow by applying an external magnetic field. The on-chip deflection of particles was compared to data provided by the manufacturers and magnetisation data obtained from vibrating sample magnetometer (VSM) measurements. Additionally, the extent of deflection was examined over a range of temperatures. Deflection distances were found to increase significantly with increasing temperature. Further to this, a separation of 2.8 and 1.0 μm magnetic particles was performed at different temperatures. Separation resolution was found to improve at higher temperatures. Hence, temperature manipulation provides a simple and effective means for improving a magnetic separation or for controlling the angle at which a particle is deflected from its hydrodynamic flow path. 相似文献
74.
Ian W. Hamley Ben M. D. O'Driscoll Gudrun Lotze Claire Moulton Jürgen Allgaier Henrich Frielinghaus 《Macromolecular rapid communications》2009,30(24):2141-2146
The phase diagram of a series of poly(1,2‐octylene oxide)–poly(ethylene oxide) (POO–PEO) diblock copolymers is determined by small‐angle X‐ray scattering. The Flory–Huggins interaction parameter was measured by small‐angle neutron scattering. The phase diagram is highly asymmetric due to large conformational asymmetry that results from the hexyl side chains in the POO block. Non‐lamellar phases (hexagonal and gyroid) are observed near fPEO = 0.5, and the lamellar phase is observed for fPEO ≥ 0.5.
75.
Dr. Damien Lhenry Dr. Manuel Larrouy Dr. Claire Bernhard Dr. Victor Goncalves Dr. Olivier Raguin Dr. Peggy Provent Dr. Mathieu Moreau Dr. Bertrand Collin Dr. Alexandra Oudot Dr. Jean‐Marc Vrigneaud Dr. François Brunotte Dr. Christine Goze Prof. Franck Denat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13091-13099
In molecular imaging, multimodal imaging agents can provide complementary information, for improving the accuracy of disease diagnosis or enhancing patient management. In particular, optical/nuclear imaging may find important preclinical and clinical applications. To simplify the preparation of dual‐labeled imaging agents, we prepared versatile monomolecular multimodal imaging probe (MOMIP) platforms containing both a fluorescent dye (BODIPY) and a metal chelator (polyazamacrocycle). One of the MOMIP was conjugated to a cyclopeptide (i.e., octreotide) and radiolabeled with 111In. In vitro and in vivo studies of the resulting bioconjugate were conducted, highlighting the potential of these BODIPY‐based bimodal probes. This work also confirmed that the biovector and/or the bimodal probes must be chosen carefully, due to the impact of the MOMIP on the overall properties of the resulting imaging agent. 相似文献
76.
Wipf P Coleman CM Janjic JM Iyer PS Fodor MD Shafer YA Stephenson CR Kendall C Day BW 《Journal of combinatorial chemistry》2005,7(2):322-330
Cascade reactions of internal and terminal alkynes, zirconocene hydrochloride, dimethylzinc, and phosphinoyl imines (prepared in one step from aldehydes and diphenylphosphinoyl amide) lead to allylic phosphinoyl amides after aqueous workup. Microwave acceleration allows the completion of this one-pot reaction sequence in 10 min. These allylic amides can be converted into a variety of derivatives, including carbamates and sulfonamides, or reacted prior to workup with diiodomethane to give novel C-cyclopropylalkylamides. A solution-phase "libraries from libraries" approach was used to generate an intermediate 20-member library which was subsequently expanded to a 100-member library by a series of N-functionalizations. The biological activity was evaluated in an assay for competitive binding to the estrogen receptor (ERalpha), revealing three potent lead compounds of a new structural type. 相似文献
77.
Pizzey CL Jewell CM Hays ME Lynn DM Abbott NL Kondo Y Golan S Talmon Y 《The journal of physical chemistry. B》2008,112(18):5849-5857
We report characterization of the nanostructures of complexes formed between the redox-active lipid bis(n-ferrocenylundecyl)dimethylammonium bromide (BFDMA) and DNA using small-angle neutron scattering (SANS) and cryogenic transmission electron microscopy (cryo-TEM). A particular focus was directed to the influence of lipid oxidation state (where reduced BFDMA has a net charge of +1 and oxidized BFDMA has a charge of +3) on the nanostructures of the solution aggregates formed. Complexes were characterized over a range of charge ratios of reduced BFDMA to DNA (1.1:1, 2.75:1, and 4:1) in solutions of 1 mM Li2SO4. For these complexes, a single peak in the SANS data at 1.2 nm(-1) indicated that a nanostructure with a periodicity of 5.2 nm was present, similar to that observed with complexes of the classical lipids DODAB/DOPE and DNA (multilamellar spacing of 7.0 nm). The absence of additional Bragg peaks in all the SANS data indicated that the periodicity did not extend over large distances. Both inverse Fourier transform analysis and form factor fitting suggested formation of a multilamellar vesicle. These results were confirmed by cryo-TEM images in which multilamellar complexes with diameters between 50 and 150 nm were observed with no more than seven lamellae per aggregate. In contrast to complexes of reduced BFDMA and DNA, Bragg peaks were absent in SANS spectra of complexes formed by oxidized BFDMA and DNA at all charge ratios investigated. The low-q behavior of the SANS data obtained using oxidized BFDMA and DNA complexes suggested that large, loose aggregates were formed, consistent with complementary cryo-TEM images showing predominantly loose disordered aggregates. Some highly ordered spongelike and cubic phase nanostructures were also detected in cryo-TEM images. We conclude that control of BFDMA oxidation state can be used to manipulate the nanostructures of lipid-DNA complexes formed using BFDMA. 相似文献
78.
Carter CL McLeod CW Bunch J 《Journal of the American Society for Mass Spectrometry》2011,22(11):1991-1998
Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a valuable tool for the analysis of molecules
directly from tissue. Imaging of phospholipids is gaining widespread interest, particularly as these lipids have been implicated
in a variety of pathologic processes. Formalin fixation (FF) is the standard protocol used in histology laboratories worldwide
to preserve tissue for analysis, in order to aid in the diagnosis and prognosis of diseases. This study assesses MALDI imaging
of phospholipids directly in formalin fixed tissue, with a view to future analysis of archival tissue. This investigation
proves the viability of MALDI-MSI for studying the distribution of lipids directly in formalin fixed tissue, without any pretreatment
protocols. High quality molecular images for several phosphatidylcholine (PC) and sphingomyelin (SM) species are presented.
Images correspond well with previously published data for the analysis of lipids directly from freshly prepared tissue. Different
ionization pathways are observed when analyzing fixed tissue compared with fresh, and this change was found to be associated
with formalin buffers employed in fixation protocols. The ability to analyze lipids directly from formalin fixed tissue opens
up new doors in the investigation of disease profiles. Pathologic specimens taken for histologic investigation can be analyzed
by MALDI-MS to provide greater information on the involvement of lipids in diseased tissue. 相似文献
79.
Tar produced during biomass steam reforming is a complex mixture of single to multiple ring aromatic compounds and it is necessary to eliminate them in order to prevent any condensation-polymerisation problem. Tar steam reforming leads to additional hydrogen that improves gas production. Previous works have shown that olivine was active in tar removal during biomass gasification and the iron distribution into the mineral different phases has a real influence on its efficiency. A Fe/olivine catalytic system has been designed to study tar steam reforming. This work presents the Fe/olivine catalyst characterizations (XRD, Mössbauer, TPR) and compares the Fe/olivine and olivine reactivity in toluene steam reforming, a tar model molecule. At 850 °C, an important conversion (95%) was observed for Fe/olivine during 7 h. The strong interaction between iron and olivine, and the equilibrium between Fe0/FeII/FeIII seem to be responsible of the catalyst activity and stability in toluene steam reforming. 相似文献
80.
Marine de Person Aude Sevestre P. Chaimbault Laurent Perrot Francis Duchiron Claire Elfakir 《Analytica chimica acta》2004,520(1-2):149-158
This paper reports the use of an on-line LC–ESI–MS/MS method for the identification and quantification of di- and tripeptides in champagne wine without laborious sample pretreatment. The identification of these compounds, in their underivatised form, is based on identical retention times and ESI–MS spectra to those of reference standards. The presence of nine dipeptides (Arg–Ile, Ile–Arg, Ile–Val, Lys–Phe, Lys–Tyr, Phe–Lys, Tyr–Gln, Tyr–Lys, Val–Ile) and the absence of two tripeptides (Phe–Arg–Arg and Lys–Met–Asn) have been evidenced in the matrix. Calibration curves for each analyte were established using Phe–Arg as internal standard. The calibration curves were linear in the concentration range 0.1–10 mg L−1 with a determination coefficient, r2, better than 0.992. The accuracy for the calibration standard was estimated at between 92 and 102%. This method allows high recovery and satisfies the necessary requirements with respect to accuracy, repeatability and sensitivity. The first application of this analytical method to the measurement of di- and tri-peptides in different vintages of champagne wine is reported. Compositional changes in the peptides occurred depending on the vintage. 相似文献