Nature's catalysts are specifically evolved to carry out efficient and selective reactions. Recent developments in biotechnology have allowed the rapid optimization of existing enzymes for enantioselective processes. However, the ex nihilo creation of catalytic activity from a noncatalytic protein scaffold remains very challenging. Herein, we describe the creation of an artificial enzyme upon incorporation of a vanadyl ion into the biotin-binding pocket of streptavidin, a protein devoid of catalytic activity. The resulting artificial metalloenzyme catalyzes the enantioselective oxidation of prochiral sulfides with good enantioselectivities both for dialkyl and alkyl-aryl substrates (up to 93% enantiomeric excess). Electron paragmagnetic resonance spectroscopy, chemical modification, and mutagenesis studies suggest that the vanadyl ion is located within the biotin-binding pocket and interacts only via second coordination sphere contacts with streptavidin. 相似文献
A comparison between a set-valued Gould type and simple Birkhoff integrals of bf(X)-valued multifunctions with respect to a non-negative set function is given. Relationships among them and Mc Shane multivalued integrability is given under suitable assumptions. 相似文献
Incorporation of biotinylated racemic three-legged d6-piano stool complexes in streptavidin yields enantioselective transfer hydrogenation artificial metalloenzymes for the reduction of ketones. Having identified the most promising organometallic catalyst precursors in the presence of wild-type streptavidin, fine-tuning of the selectivity is achieved by saturation mutagenesis at position S112. This choice for the genetic optimization site is suggested by docking studies which reveal that this position lies closest to the biotinylated metal upon incorporation into streptavidin. For aromatic ketones, the reaction proceeds smoothly to afford the corresponding enantioenriched alcohols in up to 97% ee (R) or 70% (S). On the basis of these results, we suggest that the enantioselection is mostly dictated by CH/pi interactions between the substrate and the eta6-bound arene. However, these enantiodiscriminating interactions can be outweighed in the presence of cationic residues at position S112 to afford the opposite enantiomers of the product. 相似文献
For what we believe to be the first time, digital holographic microscopy is applied to perform optical diffraction tomography of a pollen grain. Transmission phase images with nanometric axial accuracy are numerically reconstructed from holograms acquired for different orientations of the rotating sample; then the three-dimensional refractive index spatial distribution is computed by inverse radon transform. A precision of 0.01 for the refractive index estimation and a spatial resolution in the micrometer range are demonstrated. 相似文献
The paper presents the synthesis, characterization, and in vitro cytotoxicity tests of Fe3O4 magnetic nanoclusters coated with ethylenediaminetetraacetic acid disodium salt (EDTA). Electron microscopy analysis (SEM) evidences that magnetite nanoparticles are closely packed into the clusters stabilized with EDTA with well-defined near spherical shapes and sizes in the range 100–200 nm. From XRD measurements, we determined the mean size of the crystallites inside the magnetic cluster about 36 nm. The saturation magnetization determined for the magnetic clusters stabilized with EDTA has high value, about 81.7 emu/g at 300 K. X-ray photoelectron spectroscopy has been used to determine both the elemental and chemical structure of the magnetic cluster surface. In vitro studies have shown that the magnetic clusters at low doses did not induce toxicity on human umbilical vein endothelial cells or lesions of the cell membrane. In contrast, at high doses, the magnetic clusters increased the lipid peroxidation and reduced the leakage of a cytoplasmic enzyme, lactate dehydrogenase (LDH), in parallel with increasing the antioxidant defense.
A selenium analogue of amino-D-luciferin, aminoseleno-D-luciferin, is synthesized and shown to be a competent substrate for the firefly luciferase enzyme. It has a red-shifted bioluminescence emission maximum at 600?nm and is suitable for bioluminescence imaging studies in living subjects. 相似文献
The purpose of this article is to emphasize that new nanomaterials offer a number of attractive alternatives for solar energy
use in wastewater photocatalysis. The wastewater from the textile industry contains dyes and heavy metals. Thin films of cadmium
doped TiO2 (Cd-TiO2) were coated by a doctor blade using TiO2 Degussa P25 and cadmium precursor (cadmium nitrate). The photocatalytic efficiency of cadmium doped TiO2 is strongly influenced by crystal structure, particle size, particle morphology, porosity and doping. The pore size distribution
and the roughness analysis have been studied by the atomic force microscopy (AFM) of the thin films. The photocatalytic activity
of the samples was tested in Methyl orange and Methylene blue photodegradation. Cadmium doped TiO2 catalyst does not significantly decrease the efficiency of photodegradation processes, and, in some situations, improves
dye photodegradation. 相似文献
Summary In this paper the internal approximation of a quasi-variational inequality is considered. An algorithm of Bensoussan-Lions type is proposed for which the convergence is proved. These results are applied to Signorini problem with friction for which two error estimates and numerical examples are also given. 相似文献
We calculate the loss induced in a single-mode rectangular optical waveguide by the presence of a second waveguide, perpendicular to the first, which crosses over the first waveguide at a variable distance d. Our calculation is applied to the analysis of several doped silica waveguides of practical importance for optical circuit design. 相似文献
Natural products black cumin—Nigella sativa (N. sativa) and wild garlic—Allium ursinum (AU) are known for their potential role in reducing cardiovascular risk factors, including antracycline chemotherapy. Therefore, this study investigates the effect of N. sativa and AU water and methanolic extracts in a cellular model of doxorubicin (doxo)-induced cardiotoxicity. The extracts were characterized using Ultraviolet-visible (UV-VIS) spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, Liquid Chromatography coupled with Mass Spectrometry (LC-MS) and Gas Chromatography coupled with Mass Spectrometry (GC-MS) techniques. Antioxidant activity was evaluated on H9c2 cells. Cytosolic and mitochondrial reactive oxygen species (ROS) release was evaluated using 2′,7′-dichlorofluorescin-diacetate (DHCF-DA) and mitochondria-targeted superoxide indicator (MitoSOX red), respectively. Mitochondrial membrane depolarization was evaluated by flow cytometry. LC-MS analysis identified 12 and 10 phenolic compounds in NSS and AU extracts, respectively, with flavonols as predominant compounds. FT-IR analysis identified the presence of carbohydrates, amino acids and lipids in both plants. GC-MS identified the sulfur compounds in the AU water extract. N. sativa seeds (NSS) methanolic extract had the highest antioxidant activity reducing both intracellular and mitochondrial ROS release. All extracts (excepting AU methanolic extract) preserved H9c2 cells viability. None of the investigated plants affected the mitochondrial membrane depolarization. N. sativa and AU are important sources of bioactive compounds with increased antioxidant activities, requiring different extraction solvents to obtain the pharmacological effects. 相似文献