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161.
    
Herein we report the isolation and characterization of aminal intermediates in the organocatalytic α‐chlorination of aldehydes. These species are stable covalent ternary adducts of the substrate, the catalyst and the chlorinating reagent. NMR‐assisted kinetic studies and isotopic labeling experiments with the isolated intermediate did not support its involvement in downstream stereoselective processes as proposed by Blackmond. By tuning the reactivity of the chlorinating reagent, we were able to suppress the accumulation of rate‐limiting off‐cycle intermediates. As a result, an efficient and highly enantioselective catalytic system with a broad functional group tolerance was developed.  相似文献   
162.
    
Drawing inspiration from the structural features of some natural polyphenols, the synthesis of two different model compounds as potential inhibitors of HIV integrase (IN) has been described. The former was characterised by a diketo acid (DKA) bioisostere, such as a β-hydroxycarbonyl moiety, between two fragments containing aromatic groups, while in the latter an epoxide linked two polyoxygenated aromatic residues. The moieties present in the structures are thought to function by chelating divalent metal ions on the enzyme catalytic site. Overall, 10 compounds were prepared and some of that submitted to molecular modelling studies (to investigate their interactions with the active site of IN), to metal titration studies (to detect their chelating capability) and to biological assays.  相似文献   
163.
    
Tailored Forming is a complex process joining two materials before forming. Especially the joining zone of the hybrid solid component is a possible weakness. Hence, our goal is to predict and adjust the thermomechanical material behaviour of the joining zone during and after the tailored forming process. The hybrid solid components studied in this work are composed of the aluminium alloy EN AW‐6082 and the steel 20MnCr5. Metallurgical investigations on both materials show a polycrystalline microstructure. In the steel component, the two constituents ferrite and pearlite can be found with nearly the same volume fraction and randomly distributed grains. Furthermore, between the two bulk materials aluminium and steel, a thin layer of brittle intermetallic phases can be observed. In this work, the intermetallic phases are considered to behave purely thermoelastic, whereas the material model for aluminium, ferrite and pearlite represents thermoplastic material behaviour. We present the dislocation density based models for the thermoplastic materials formulated in a continuum mechanics framework. Thereby, different mechanisms of annihilation contributing to the evolution equation for the internal variables will be on focus.  相似文献   
164.
Cyclosporine, tacrolimus, sirolimus, and everolimus are commonly used immunosuppressants following organ transplantation. Their monitoring is used to determine the optimal dose for therapeutic effectiveness and minimize toxicity. High-performance liquid chromatographic–tandem mass spectrometry with positive electrospray ionization and multiple reaction monitoring mode was validated for the determination of cyclosporine A, tacrolimus, sirolimus, and everolimus in whole blood. A C18 analytical column was employed with a gradient elution of pH 4.0 aqueous 10?mmol/L ammonium acetate and acetonitrile. For the pretreatment of whole blood, simple protein precipitation was used with methanol:zinc sulfate. The calibration curves were linear from 20.0 to 1000?ng/mL for cyclosporine A, 1.0 to 50?ng/mL for tacrolimus and sirolimus, and 1.0 to 30?ng/mL for everolimus. The intra-assay precision and inter-assay precision were less than 15%. The method provides reliable and reproducible results according to the linearity, precision, accuracy, recovery, and matrix effects. The method has been introduced to routine clinical practice in Slovakia for the determination of immunosuppressants in patients after kidney transplantation.  相似文献   
165.
166.
    
Lasers are widely used in various manufacturing processes. In order to achieve sustainable production, it is important to reduce the environmental impact caused by the laser operation. One major improvement is the step from gas lasers to diode lasers.  相似文献   
167.
We present an extensive experimental study of mode-I, steady, slow crack dynamics in gelatin gels. Taking advantage of the sensitivity of the elastic stiffness to gel composition and history we confirm and extend the model for fracture of physical hydrogels which we proposed in a previous paper (Nature Mater. 5, 552 (2006)), which attributes decohesion to the viscoplastic pull-out of the network-constituting chains. So, we propose that, in contrast with chemically cross-linked ones, reversible gels fracture without chain scission.  相似文献   
168.
The studied ferronematic is a nematic liquid crystal (ZLI1695) of low negative anisotropy of the diamagnetic susceptibility (χa<0) doped with the magnetic particles Fe3O4. Structural instabilities are interpreted within Burylov and Raikher's theory. The high magnetic fields were oriented perpendicular (Freedericksz transition) or parallel to the initial director. Using capacitance measurements the Freedericksz threshold magnetic field of the ferronematic BFN, and the critical magnetic field Bmax, at which the initial parallel orientation between the director and the magnetic moment of magnetic particles breaks down, have been determined. The values of these quantities have been used to estimate the surface density of the anchoring energy W of liquid crystal molecules on the surface of the magnetic particles. The obtained values indicate a soft anchoring of the liquid crystal on the magnetic particles with a preferred parallel orientation of the magnetic moment of magnetic particles and the director.  相似文献   
169.
170.
Poly(ethylene glycol) (PEG)-containing magnetic fluids - magnetite (Fe3O4) stabilized by sodium oleate - were prepared. Magnetic measurements confirmed superparamagnetic behaviour at room temperature. The structure of that kind of magnetic fluid was characterized using different techniques, including electron microscopy, photon cross correlation spectroscopy and small-angle neutron scattering, while the adsorption of PEG on magnetic particles was analyzed by differential scanning calorimetry and Fourier transform infrared spectroscopy. From the in vitro toxicity tests it was found that a magnetic fluid containing PEG (MFPEG) partially inhibited the growth of cancerous B16 cells at the highest tested dose (2.1 mg/ml of Fe3O4 in MFPEG).  相似文献   
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