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941.
LC method with the newly introduced second‐generation monolithic silica RP‐18e column has been developed for the separation of FeIII(salophene) and four methoxy‐substituted FeIII(salophene) complexes. The method has been validated for the quantitation of FeIII(4‐OMe‐salophene), a highly active anticancer substance in vitro, bound to serum albumin. Our routinely used high‐resolution continuum‐source atomic absorption spectroscopy method based on the determination of the central iron atom was unsuitable in this case because serum originally contains significant amounts of iron as revealed by a blank sample of serum albumin. The developed LC method depends on detecting the whole complex rather than the bound iron. Two morphologically different first‐ and second‐generation HPLC monolithic columns have been compared for this purpose. The newly introduced second‐generation monolithic silica column Chromolith® HighResolution RP‐18e column (100 × 4.6 mm, Merck) separated the mixture successful within 13 min. A mobile phase consisting of 25 mM phosphate buffer pH 3/methanol (60:40, v/v) was used at a flow rate of 1 mL/min. The dynamic linear working range of the calibration curve for FeIII(4‐OMe‐salophene) was found to be between 1 and 200 μg/mL. Detection and quantitation limits were 0.3 and 1 μg/mL, respectively. 相似文献
942.
Tjasa Vrlinic Dominique Debarnot Gilbert Legeay Arnaud Coudreuse Benaissa El Moualij Willy Zorzi Armand Perret‐Liaudet Isabelle Quadrio Miran Mozetic Fabienne Poncin‐Epaillard 《Macromolecular bioscience》2012,12(6):830-839
New non‐fouling tubes are developed and their influence on the adhesion of neuroproteins is studied. Recombinant prion proteins are considered as a single component representative of hydrophobic proteins. Samples are stored for 24 h at 4 °C in tubes coated with two different coatings: poly(N‐isopropylacrylamide) as a hydrophilic surface and a plasma‐fluorinated coating as a hydrophobic one. The protein adhesion is monitored by ELISA tests, XPS and confocal microscopy. It appears that the highest recovery of recombinant prion protein in the liquid phase is obtained with the hydrophilic surface while the hydrophobic character of the storage tube induces an important amount of biological loss. However, the recovery is not complete even for tubes coated with poly(N‐isopropylacrylamide).
943.
Dr. Hongpeng Jia Belinda Schmid Dr. Shi‐Xia Liu Michael Jaggi Philippe Monbaron Dr. Sheshanath V. Bhosale Shadi Rivadehi Prof. Steven J. Langford Dr. Lionel Sanguinet Dr. Eric Levillain Dr. Mohamed E. El‐Khouly Prof. Ysushi Morita Prof. Shunichi Fukuzumi Prof. Silvio Decurtins 《Chemphyschem》2012,13(14):3370-3382
A tetrathiafulvalene (TTF) donor is annulated to porphyrins (P) via quinoxaline linkers to form novel symmetric P–TTF–P triads 1 a – c and asymmetric P–TTF dyads 2 a , b in good yields. These planar and extended π‐conjugated molecules absorb light over a wide region of the UV/Vis spectrum as a result of additional charge‐transfer excitations within the donor–acceptor assemblies. Quantum‐chemical calculations elucidate the nature of the electronically excited states. The compounds are electrochemically amphoteric and primarily exhibit low oxidation potentials. Cyclic voltammetric and spectroelectrochemical studies allow differentiation between the TTF and porphyrin sites with respect to the multiple redox processes occurring within these molecular assemblies. Transient absorption measurements give insight into the excited‐state events and deliver corresponding kinetic data. Femtosecond transient absorption spectra in benzonitrile may suggest the occurrence of fast charge separation from TTF to porphyrin in dyads 2 a , b but not in triads 1 a – c . Clear evidence for a photoinduced and relatively long lived charge‐separated state (385 ps lifetime) is obtained for a supramolecular coordination compound built from the ZnP–TTF dyad and a pyridine‐functionalized C60 acceptor unit. This specific excited state results in a (ZnP–TTF)?+ ??? (C60py)?? state. The binding constant of ZnII ??? py is evaluated by constructing a Benesi–Hildebrand plot based on fluorescence data. This plot yields a binding constant K of 7.20×104 M ?1, which is remarkably high for bonding of pyridine to ZnP. 相似文献
944.
Theberge AB Mayot E El Harrak A Kleinschmidt F Huck WT Griffiths AD 《Lab on a chip》2012,12(7):1320-1326
This paper presents a droplet-based microfluidic platform for miniaturized combinatorial synthesis. As a proof of concept, a library of small molecules for early stage drug screening was produced. We present an efficient strategy for producing a 7 × 3 library of potential thrombin inhibitors that can be utilized for other combinatorial synthesis applications. Picolitre droplets containing the first type of reagent (reagents A(1), A(2), …, A(m)) were formed individually in identical microfluidic chips and then stored off chip with the aid of stabilizing surfactants. These droplets were then mixed to form a library of droplets containing reagents A(1-m), each individually compartmentalized, which was reinjected into a second microfluidic chip and combinatorially fused with picolitre droplets containing the second reagent (reagents B(1), B(2), …, B(n)) that were formed on chip. The concept was demonstrated with a three-component Ugi-type reaction involving an amine (reagents A(1-3)), an aldehyde (reagents B(1-7)), and an isocyanide (held constant), to synthesize a library of small molecules with potential thrombin inhibitory activity. Our technique produced 10(6) droplets of each reaction at a rate of 2.3 kHz. Each droplet had a reaction volume of 3.1 pL, at least six orders of magnitude lower than conventional techniques. The droplets can then be divided into aliquots for different downstream screening applications. In addition to medicinal chemistry applications, this combinatorial droplet-based approach holds great potential for other applications that involve sampling large areas of chemical parameter space with minimal reagent consumption; such an approach could be beneficial when optimizing reaction conditions or performing combinatorial reactions aimed at producing novel materials. 相似文献
945.
Three different strategies for cucurbit[8]uril immobilization on a glassy carbon electrode have been assayed. The electrochemical properties of the resulting modified electrodes in solutions containing neutral, positively and negatively charged potential cucurbit[8]uril guests were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The comparison of the electrochemical behaviour exhibited by the unmodified electrodes against various probes, with respect to that of each modified electrode, resulted in an appropriate method to choose among different strategies for the development of electrochemical sensors. These sensors are based on the incorporation of the cucurbit[8]uril molecular selection properties that depend on the chemical characteristics of the potential analytes. Furthermore, atomic force microscopy was employed for the characterization of the different surfaces developed. 相似文献
946.
The kinetics of the homogeneous acylation of microcrystalline cellulose, MCC, with carboxylic acid anhydrides with different
acyl chain-length (Nc; ethanoic to hexanoic) in LiCl/N,N-dimethylacetamide have been studied by conductivity measurements from 65 to 85 °C. We have employed cyclohexylmethanol, CHM,
and trans-1,2-cyclohexanediol, CHD, as model compounds for the hydroxyl groups of the anhydroglucose unit of cellulose. The ratios
of rate constants of acylation of primary (CHM; Prim-OH) and secondary (CHD; Sec-OH) groups have been employed, after correction,
in order to split the overall rate constants of the reaction of MCC into contributions from the discrete OH groups. For the model compounds, we have found
that k(Prim-OH)/k(Sec-OH) > 1, akin to reactions of cellulose under heterogeneous conditions; this ratio increases as a function of increasing Nc. The overall, and partial rate constants of the acylation of MCC decrease from ethanoic- to butanoic-anhydride and then
increase for pentanoic- and hexanoic anhydride, due to subtle changes in- and compensations of the enthalpy and entropy of
activation. 相似文献
947.
El Khatib M Elagawany M Jabeen F Todadze E Bol'shakov O Oliferenko A Khelashvili L el-Feky SA Asiri A Katritzky AR 《Organic & biomolecular chemistry》2012,10(25):4836-4838
Chemical ligation via O- to N-acyl transfer of O-acylated serine containing peptides affords serine containing native peptides via 8- and 11-membered cyclic transition states opening the door to a wide variety of potential applications to peptide elaboration. The feasibility of these traceless chemical ligations is feasible as supported by computation. 相似文献
948.
T. Abdallah T.A. El‐Brolosy M. B. Mohamed K. Easawi S. Negm H. Talaat 《Journal of Raman spectroscopy : JRS》2012,43(12):1924-1930
Surface enhanced Raman scattering (SERS) of adsorbed molecule on colloidal gold nanoparticles of different shapes, namely nanospheres (NSs), nanorods (NRs), and nanoprisms (NPs) as well as the three NPs arrays of different interstice prepared by NS lithography, are studied with incident wavenumbers in the near‐dipole and near‐quadrpole regions of the nanoparticles. In the colloidal gold nanoparticles, the SERS enhancement is the largest for the sharp tip followed by the truncated tip NPs, then the NRs and least enhancement for the NSs. This decreasing order of enhancement occurs although the incident wavenumber was near the dipole resonance of NSs and the quadrupole resonance for the NPs. These varied enhancements are explained in part as due to the binding energies of the nanocrystal facets, but the larger contribution results from the plasmon electromagnetic fields. A parallel finite difference time domain (FDTD) calculations were carried out, which corporate the experimental results and show agreement with ratios of the SERS enhancement for the different shapes. The normalized SERS intensity for NPs of different interstice distances show a sharp rise with the decrease of the interstice distances because of interparticle dipolar and quadrupolar coupling as evidenced also by FDTD calculations. Furthermore, these calculations show that the enhancement is polarization independent for an incident wavelength near quadrupole resonance but polarization dependent for an incident wavelength near the plasmon dipole transition. In the last case, the enhancement is larger by an order of magnitude for a polarization parallel to the NPs bisector than for polarization normal to the bisector with no hot spots for the relatively large interstice dimensions used. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
949.
In this note, we first give a quick presentation of the supergeometry underlying supergravity theories, using an intrinsic differential geometric language. For this, we adopt the point of view of Cartan geometries, and rely as well on the work of John Lott, who has found a unified geometrical interpretation of the torsion constraints for many supergravity theories, based on the use of H-structures. In this framework, the constraints amount to requiring first-order integrability of H-structures, for a specific supergroup H.The supergroup H used by Lott is not the usual diagonal representation of the Lorentz group on superspace, but an extension of the latter. This extension appears to be natural and it can be related to the super-Poincaré group. We also observe that the constraints arising from the requirement of first-order integrability have basically the same form, in any spacetime dimension.Looking at supergravity from an affine viewpoint (i.e. as a gauge theory for the super-Poincaré group), we show that requiring first-order integrability amounts to requiring the equivalence, up to gauge transformations, between infinitesimal gauge supertranslations acting on the supervielbein and infinitesimal superdiffeomorphisms acting on the supervielbein.The latter action is performed through a covariant Lie derivative, whose expression involves naturally the supertorsion tensor. We use this expression to show that the term added to the spin connection, in the supercovariant derivative of d=11 supergravity, has a natural superspace origin. In particular, the 4-form field strength is related to a specific component of the supertorsion tensor.We conclude by some general remarks concerning Killing spinors in geometry and supergravity, discussing their possible interpretations, as Killing vector fields on a specific supermanifold on one hand, and as parallel spinors for an appropriate connection on the other hand. We show that this last interpretation is very natural from the point of view of Klein and Cartan geometries. 相似文献
950.
O.M. Lemine K. Omri B. Zhang L. El Mir M. Sajieddine A. Alyamani M. Bououdina 《Superlattices and Microstructures》2012
Magnetite (Fe3O4) nanoparticles were successfully synthesized by a sol–gel method. The obtained nanoparticles were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive analysis by X-ray (EDAX), transmission electron microscopy (TEM), superconducting quantum interference device (SQUID) and Mössbauer spectrometry. XRD and Mössbauer measurements indicate that the obtained nanoparticles are single phase. TEM analysis shows the presence of spherical nanoparticles with homogeneous size distribution of about 8 nm. Room temperature ferromagnetics behavior was confirmed by SQUID measurements. The mechanism of nanoparticles formation and the comparison with recent results are discussed. Finally, the synthesized nanoparticles present a potential candidate for hyperthermia application given their saturation magnetization. 相似文献