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Andrew P. Vogt Vanessa Trouillet Alexandra M. Greiner Michael Kaupp Udo Geckle Leonie Barner Thorsten Hofe Christopher Barner‐Kowollik 《Macromolecular rapid communications》2012,33(13):1108-1113
Boronic acid‐functionalized microspheres are prepared for the first time via mild epoxide ring opening based on porous cross‐linked polymeric microspheres (diameter ≈ 10 μm, porosity ≈ 1000 Å). Quantitative chemical analysis by XPS and EA evidences that there is a greater functionalization with boronic acid when employing a sequential synthetic method [1.7 atom% boron (XPS); 1.12 wt% nitrogen (EA)] versus a one‐pot synthetic method [0.2 atom% boron (XPS); 0.60 wt% nitrogen (EA)] yielding grafting densities ranging from approximately 2.5 molecules of boronic acid per nm2 to 1 molecule of boronic acid per nm2, respectively. Furthermore, the boronic acid‐functionalized microspheres are conjugated with a novel fluorescent glucose molecule demonstrating a homogeneous spatial distribution of boronic acid. 相似文献
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Matthew R. Buck Prof. Raymond E. Schaak 《Angewandte Chemie (International ed. in English)》2013,52(24):6154-6178
New synthetic innovations are rapidly being developed to address the demand for complex, next‐generation nanomaterials with rigorously controlled architectures and interfaces. This Review highlights key strategies for the chemical transformation and stepwise synthesis of multicomponent inorganic nanostructures, with the existing nanoscale transformations categorized into classes of reactions that are related to those used in the synthesis of organic molecules. The application of concepts used in molecular synthesis—including site‐selectivity, regio‐ and chemoselectivity, orthogonal reactivity, coupling reactions, protection/deprotection strategies, and procedures for separation and purification—to nanoscale systems is emphasized. Collectively, the resulting synthetic concept represents an emerging model for the synthesis of complex inorganic nanostructures on the basis of the guiding principles that underpin the multistep total synthesis of complex organic molecules and natural products. 相似文献
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Henk M. Buck 《International journal of quantum chemistry》2010,110(7):1412-1424
We studied various identity nucleophilic substitution reactions based on an SN2 reaction profile. With calculations and experimental geometries concerning the nature of the various complexes indicated as stable, intermediate, and transition state we were able to show the additional value of van't Hoff 's tetrahedron by changing its geometry via a trigonal pyramid into a trigonal bipyramid. The ratio of the apical and the corresponding tetrahedral bond distance is then 1.333. This value has been used in general as a calibration point for the understanding of the (in)stabilities of the complex formation on the SN2 reaction coordinate. The relevance of this approach has been also proved for enzymatic reactions focused on carbon and phosphorus substrates. Furthermore, it could be established that identity proton‐in‐line displacements are fully comparable with the relocation of carbon in a nucleophilic substitution reaction as Cl? + CH3Cl. The significance of this information will afford new insight in the dynamics of a linear three‐center four‐electron complex. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
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Koeniger SL Talaty N Luo Y Ready D Voorbach M Seifert T Cepa S Fagerland JA Bouska J Buck W Johnson RW Spanton S 《Rapid communications in mass spectrometry : RCM》2011,25(4):503-510
A new quantitation method for mass spectrometry imaging (MSI) with matrix-assisted laser desorption/ionization (MALDI) has been developed. In this method, drug concentrations were determined by tissue homogenization of five 10 μm tissue sections adjacent to those analyzed by MSI. Drug levels in tissue extracts were measured by liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS). The integrated MSI response was correlated to the LC/MS/MS drug concentrations to determine the amount of drug detected per MSI ion count. The study reported here evaluates olanzapine in liver tissue. Tissue samples containing a range of concentrations were created from liver harvested from rats administered a single dose of olanzapine at 0, 1, 4, 8, 16, 30, or 100 mg/kg. The liver samples were then analyzed by MALDI-MSI and LC/MS/MS. The MALDI-MSI and LC/MS/MS correlation was determined for tissue concentrations of ~300 to 60,000 ng/g and yielded a linear relationship over two orders of magnitude (R(2) = 0.9792). From this correlation, a conversion factor of 6.3 ± 0.23 fg/ion count was used to quantitate MSI responses at the pixel level (100 μm). The details of the method, its importance in pharmaceutical analysis, and the considerations necessary when implementing it are presented. 相似文献