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141.
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Catalytically active MnOx species have been reported to form in situ from various Mn‐complexes during electrocatalytic and solution‐based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnOx catalysts form without supports in situ under photocatalytic conditions. Our most active 4MnOx catalyst (~0.84 mmol O2 mol Mn?1 s?1) forms from a Mn4O4 bearing a metal–organic framework. 4MnOx is characterized by pair distribution function analysis (PDF), Raman spectroscopy, and HR‐TEM as a disordered, layered Mn‐oxide with high surface area (216 m2g?1) and small regions of crystallinity and layer flexibility. In contrast, the SMnOx formed from Mn2+ salt gives an amorphous species of lower surface area (80 m2g?1) and lower activity (~0.15 mmol O2 mol Mn?1 s?1). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p3/2 core levels detects enriched Mn3+ and Mn2+ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria.  相似文献   
144.
A sensitive and specific liquid chromatography–electrospray ionization-tandem mass spectrometry method has been developed and validated for the identification and quantification of ursolic acid in human plasma using glycyrrhetic acid as an internal standard. The method involves extraction with methyl tert-butyl ether. The analyte was separated on a C18 column and analyzed in multiple reaction monitoring mode with a negative electrospray ionization interface using the [M–H]? ions, m/z 455.4 for ursolic acid and m/z 469.5 → m/z 425.5 for glycyrrhetic acid. The method was validated over the concentration range of 0.86–110.0 μg L?1. The intra- and inter-day precisions were less than 13.53% relative standard deviation (RSD) and the accuracy was within ?4.76% in terms of relative error (RE). The lower limit of quantification was 0.86 μg L?1 with acceptable precision and accuracy. There were almost no matrix effects. Recovery of ursolic acid from spiked drug-free plasma was higher than 68%. The method was used to study the pharmacokinetic profile of ursolic acid in human plasma after oral administration of Jieyu capsules.  相似文献   
145.
We report the use of atomic layer deposition (ALD) coating as a nanobiosensor functionalization strategy for enhanced surface immobilization that may enable higher detection sensitivity. Three kinds of ALD coating films, Al(2)O(3), TiO(2), and SiO(2), were grown on the gallium nitride nanowire (GaN NW) surfaces and characterized with high-resolution transmission electron microscopy (HRTEM) and vacuum Fourier transform infrared spectroscopy (FTIR). Results from HRTEM showed that the thicknesses of ALD-Al(2)O(3), ALD-TiO(2) and ALD-SiO(2) coatings were 4-5 nm, 5-6 nm, and 12-14 nm, respectively. Results from FTIR showed that the OH contents of these coatings were, respectively, ~6.9, ~7.4, and ~9.3 times that of piranha-treated GaN NW. Furthermore, to compare protein attachments on the different surfaces, poly(ethylene glycol) (PEG)-biotin was grafted on the OH-functionalized GaN NW surfaces through active Si-Cl functional groups. Streptavidin protein molecules were then attached to the biotin ends via specific binding. The immobilized streptavidin molecules were examined with scanning electron microscopy, HRTEM, and fluorescent imaging. Results from HRTEM and energy-dispersive X-ray revealed that the nitrogen concentrations on the three ALD coatings were significantly higher than that on the piranha-treated surface. Results from fluorescent imaging further showed that the protein attachments on the Al(2)O(3), TiO(2), and SiO(2) ALD coatings were, respectively, 6.4, 7.8, and 9.8 times that of piranha-treated surface. This study demonstrates that ALD coating can be used as a functionalization strategy for nanobiosensors because it is capable of creating functional groups with much higher density compared to widely used acid modifications, and among the three ALD coatings, ALD-SiO(2) yielded the most promising results in OH content and protein attachment.  相似文献   
146.
(-)-Alternarlactam [(-)-1], a new promising cytotoxin against two human cancer cell lines, was isolated from an endophyte culture and synthesized (along with (+)-1) from readily available starting materials. The absolute configuration, chirality-activity relevance and self-aggregation of (-)-1 were assigned by a combination of synthetic, spectroscopic and computational approaches. The full characterization of the new fungal cytotoxin may provide valuable information in the discovery of new antitumor agents.  相似文献   
147.
A genetic algorithm (GA) conformation search method is used to dock a series of flexible molecules into one of three proteins. The proteins examined are thermolysin (tmn), carboxypeptidase A (cpa), and dihydrofolate reductase (dfr). In the latter two proteins, the crystal ligand was redocked. For thermolysin, we docked eight ligands into a protein conformation derived from a single crystal structure. The bound conformations of the other ligands in tmn are known. In the cpa and dfr cases, and in seven of the eight tmn ligands, the GA docking method found conformations within 1.6 Å root mean square (rms) of the relaxed crystal conformation. © 1995 John Wiley & Sons, Inc.  相似文献   
148.
人体血中吗啡浓度的GC/MS测定法   总被引:4,自引:0,他引:4  
本实验采用磷酸可待因作内标,经液相萃取、乙酸酐衍生化处理后,用GC/MS的选择离子定量模型(SIM)测定肿瘤病人体内吗啡的血药浓度。方法的最低检出限为0.95ng/mL,在1.0~60.0ng/mL的浓度范围内,标准曲线呈良好的线性,r>0.998,日内日间误差小于9.0%,回收率达96%,已成功地应用在8例肿瘤病人口服30mg吗啡控释片的药代动力学的研究上。  相似文献   
149.
Solid complexes of lighter lanthanide nitrates with N,N′-dinaphthyl-N,N′-diphenyl-3,6-dioxaoctanediamide (DDD), Ln(NO3)3(DDD) (Ln = La---Nd, Sm) have been prepared in non-aqueous media. These complexes have been characterized by elemental analysis, conductivity measurements, IR spectra, electronic spectra and TG-DTA techniques. In all the complexes, DDD and NO3 are coordinated to the lanthanide ions as tetradentate and bidentate ligands, respectively. The differences in the IR and electronic spectra between these complexes and lanthanide nitrate complexes with N,N,N′,N′-tetraphenyl-3,6-dioxaoctanediamide (TDD) are discussed.  相似文献   
150.
Tan YL  Quanci JF 《Talanta》1985,32(7):577-578
A packed-column gas-chromatograph/mass-spectrometer (GC/MS), Hewlett-Packard 5982, was modified to accommodate fused silica capillary columns. The original GC/MS interface and chemical-ionization sample-line in the ion-source were changed to allow the end of a fused silica capillary column to enter the ion-chamber directly. For chemical-ionization operation, the reagent gas was brought into the MS through the direct-insertion probe port. The calibration compound was introduced through the electron-impact sample-inlet, which simplified the operation. The modified system yields higher sensitivity and more efficient separation, as well as simpler operation, without sacrificing any original instrument functions.  相似文献   
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