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81.
Moeser B Janoschka A Wolny JA Paulsen H Filippov I Berry RE Zhang H Chumakov AI Walker FA Schünemann V 《Journal of the American Chemical Society》2012,134(9):4216-4228
In this work, we present a study of the influence of the protein matrix on its ability to tune the binding of small ligands such as NO, cyanide (CN(-)), and histamine to the ferric heme iron center in the NO-storage and -transport protein Nitrophorin 2 (NP2) from the salivary glands of the blood-sucking insect Rhodnius prolixus. Conventional M?ssbauer spectroscopy shows a diamagnetic ground state of the NP2-NO complex and Type I and II electronic ground states of the NP2-CN(-) and NP2-histamine complex, respectively. The change in the vibrational signature of the protein upon ligand binding has been monitored by Nuclear Inelastic Scattering (NIS), also called Nuclear Resonant Vibrational Spectroscopy (NRVS). The NIS data thus obtained have also been calculated by quantum mechanical (QM) density functional theory (DFT) coupled with molecular mechanics (MM) methods. The calculations presented here show that the heme ruffling in NP2 is a consequence of the interaction with the protein matrix. Structure optimizations of the heme and its ligands with DFT retain the characteristic saddling and ruffling only if the protein matrix is taken into account. Furthermore, simulations of the NIS data by QM/MM calculations suggest that the pH dependence of the binding of NO, but not of CN(-) and histamine, might be a consequence of the protonation state of the heme carboxyls. 相似文献
82.
Mesoporous silica nanoparticles in biomedical applications 总被引:1,自引:0,他引:1
This tutorial review provides an outlook on nanomaterials that are currently being used for theranostic purposes, with a special focus on mesoporous silica nanoparticle (MSNP) based materials. MSNPs with large surface area and pore volume can serve as efficient carriers for various therapeutic agents. The functionalization of MSNPs with molecular, supramolecular or polymer moieties, provides the material with great versatility while performing drug delivery tasks, which makes the delivery process highly controllable. This emerging area at the interface of chemistry and the life sciences offers a broad palette of opportunities for researchers with interests ranging from sol-gel science, the fabrication of nanomaterials, supramolecular chemistry, controllable drug delivery and targeted theranostics in biology and medicine. 相似文献
83.
Soliton self-frequency shift (SSFS) in a photonic crystal fiber (PCF) pumped by a long-cavity mode-locked Cr:forsterite laser is integrated with second harmonic generation (SHG) in a nonlinear crystal to generate ultrashort light pulses tunable within the range of wavelengths from 680 to 1800?nm at a repetition rate of 20?MHz. The pulse width of the second harmonic output is tuned from 70 to 600?fs by varying the thickness of the nonlinear crystal, beam-focusing geometry, and the wavelength of the soliton PCF output. Wavelength-tunable pulses generated through a combination of SSFS and SHG are ideally suited for coherent Raman microspectroscopy at high repetition rates, as verified by experiments on synthetic diamond and polystyrene films. 相似文献
84.
Evgenij V. Zarudnitskii Aleksandr A. Yurchenko Anatolij S. Merkulov Marina G. Semenova Aleksandr M. Pinchuk Andrej A. Tolmachev 《Heteroatom Chemistry》2005,16(7):648-655
The reaction of phosphorus(III) halides with 6‐substituted imidazo[2,1‐b]thiazoles in the presence of bases proceeds regioselectively and affords 5‐phosphinoimidazo[2,1‐b]thiazoles, useful synthons for the preparation of various P(III) and P(V) derivatives. 5‐Phosphinoimidazo[2,1‐b]thiazoles are selectively alkylated at the phosphorus or heterocyclic nitrogen atom, depending on the alkylating agent. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:648–655, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20166 相似文献
85.
Sergei D. Kirik Ekaterina G. Yakovleva Aleksandr F. Shimanskii Yurii G. Kovalev 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(12):1367-1368
The title compound, cadmium bismuth dioxide chloride, CdBiO2Cl, was obtained as a white powder by reaction of solid BiOCl with CdO at 973 K. Ab initio crystal structure determination was carried out using X-ray powder diffraction techniques, including direct methods for atom location and Rietveld fitting for the final refinement. Being monoclinic, the crystal structure can be related to tetragonal Sillen layered phases. The main structural elements present are CdBiO2+ pleated metal–oxygen layers alternating with Cl layers along the c axis, whereas along the b axis, all atoms are on mirror planes. The formation of a strong Cd—Cl bond draws the layers together, causing layer deformation and a monoclinic distortion in the layer arrangement. 相似文献
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Aleksandr L Simonian Alexander Revzin James R WildJerry Elkind Michael V Pishko 《Analytica chimica acta》2002,466(2):201-212
The electrostatic assembly of nanocomposite thin films consisting of alternating layers of an organometallic redox polymer (RP) and oxidoreductase enzymes, glucose oxidase (GOX), lactate oxidase (LOX) and pyruvate oxidase (PYX), was investigated. Multilayer nanostructures were fabricated on gold surfaces by the deposition of an anionic self-assembled monolayer of 11-mercaptoundecanoic acid, followed by the electrostatic attachment of a cationic RP, poly(vinylpyridine Os(bis-bipyridine)2Cl-co-allylamine) (PVP-Os-AA), and anionic oxidoreductase enzymes. Surface plasmon resonance (SPR) spectroscopy, Fourier transform infrared external reflection spectroscopy (FT-IR-ERS) and electrochemistry were employed to characterize the assembly of these nanocomposite films. The surface concentration of GOX was found to be 2.4 ng/mm2 for the first enzyme layer and 1.96 ng/mm2 for the second enzyme layer, while values of 10.7 and 1.3 ng/mm2 were obtained for PYX and LOX, respectively. The apparent affinity constant for GOX adsorption was found to be 8×107 M−1. FT-IR-ERS was used to verify the incorporation of GOX and its conformational stability inside of these nanocomposite thin films. An SPR instrument with a flow-through cell was modified by additions of Ag/AgCl reference and Pt counter electrodes, with the gold-coated SPR surface film serving as the working electrode. This enabled real-time observation of the assembly of sensing components and immediate, in situ electrochemical verification of substrate-dependent current upon the addition of enzyme to the multilayer structure. A glucose-dependant amperometric response with sensitivity of 0.197 μA/cm2/mM for a linear range of 1-10 mM of glucose was obtained. The SPR and FT-IR-ERS studies also showed no desorption of polymer or enzyme from the nanocomposite RP-GOX structure when stored in aqueous environment occurred over the period of 3 weeks, suggesting that decreasing substrate sensitivity with time was due to loss of enzymatic activity rather than loss of film compounds from the nanostructure. 相似文献