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41.
Rai BK Durbin SM Prohofsky EW Sage JT Ellison MK Roth A Scheidt WR Sturhahn W Alp EE 《Journal of the American Chemical Society》2003,125(23):6927-6936
Detailed Fe vibrational spectra have been obtained for the heme model complex [Fe(TPP)(CO)(1-MeIm)] using a new, highly selective and quantitative technique, Nuclear Resonance Vibrational Spectroscopy (NRVS). This spectroscopy measures the complete vibrational density of states for iron atoms, from which normal modes can be calculated via refinement of the force constants. These data and mode assignments can reveal previously undetected vibrations and are useful for validating predictions based on optical spectroscopies and density functional theory, for example. Vibrational modes of the iron porphyrin-imidazole compound [Fe(TPP)(CO)(1-MeIm)] have been determined by refining normal mode calculations to NRVS data obtained at an X-ray synchrotron source. Iron dynamics of this compound, which serves as a useful model for the active site in the six-coordinate heme protein, carbonmonoxy-myoglobin, are discussed in relation to recently determined dynamics of a five-coordinate deoxy-myoglobin model, [Fe(TPP)(2-MeHIm)]. For the first time in a six-coordinate heme system, the iron-imidazole stretch mode has been observed, at 226 cm(-)(1). The heme in-plane modes with large contributions from the nu(42), nu(49), nu(50), and nu(53) modes of the core porphyrin are identified. In general, the iron modes can be attributed to coupling with the porphyrin core, the CO ligand, the imidazole ring, and/or the phenyl rings. Other significant findings are the observation that the porphyrin ring peripheral substituents are strongly coupled to the iron doming mode and that the Fe-C-O tilting and bending modes are related by a negative interaction force constant. 相似文献
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Gryko DT Clausen C Roth KM Dontha N Bocian DF Kuhr WG Lindsey JS 《The Journal of organic chemistry》2000,65(22):7345-7355
The attachment of redox-active molecules such as porphyrins to an electroactive surface provides an attractive approach for electrically addressable molecular-based information storage. Porphyrins are readily attached to a gold surface via thiol linkers. The rate of electron transfer between the electroactive surface and the porphyrin is one of the key factors that dictates suitability for molecular-based memory storage. This rate depends on the type and length of the linker connecting the thiol unit to the porphyrin. We have developed different routes for the preparation of thiol-derivatized porphyrins with eight different linkers. Two sets of linkers explore the effects of linker length and conjugation, with one set comprising phenylethyne units and one set comprising alkyl units. One electron-deficient linker has four fluorine atoms attached directly to a thiophenyl unit. To facilitate the synthesis of the porphyrins, convenient routes have been developed to a wide range of aldehydes possessing a protected S-acetylthio group. An efficient synthesis of 1-(S-acetylthio)-4-iodobenzene also has been developed. A set of porphyrins, each bearing one S-acetyl-derivatized linker at one meso position and mesityl moieties at the three remaining meso positions, has been synthesized. Altogether seven new aldehydes, eight free base porphyrins and eight zinc porphyrins have been prepared. The zinc porphyrins bearing the different linkers all form self-assembled monolayers (SAMs) on gold via in situ cleavage of the S-acetyl protecting group. The SAM of each porphyrin is electrochemically robust and exhibits two reversible oxidation waves. 相似文献
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William W. Ward Hugh J. Prentice Amy F. Roth Chris W. Cody Sue C. Reeves 《Photochemistry and photobiology》1982,35(6):803-808
Abstract— In the jellyfish Aequorea, the green-fluorescent protein (GFP) functions as the in vivo bio-luminescence emitter via energy transfer from the photoprotein aequorin. Accumulated evidence has indicated that the Aequorea GFP is a relatively inflexible protein. Present evidence, however, indicates that the chromophore environment is readily accessible to a variety of external perturbants. Native Aequorea GFP has an absorbance maximum at 395 nm and a shoulder at 470 nm. In low ionic strength buffer at neutral pH and room temperature the 395/470 nm absorbance ratio is about 2.0. We show that this ratio is highly variable depending upon temperature, ionic strength, protein concentration, and pH. A maximum ratio of 6.5 (at a protein concentration of 18.6 mg/m/) and minimum of 0.42 (at a pH of 12.2) have been measured. In the latter case, the resulting absorption and excitation spectra resemble those of Renilla GFP in spectral shape (but not wavelength maximum). In all cases as the perturbant is varied the resulting spectra pass through a sharp isosbestic point, suggesting a relatively simple two-state mechanism. These spectral perturbations are fully reversible. On the basis of these results, we suggest that the chromophore binding site is conformationally flexible. pH-Dependent changes in the near-UV and visible circular dichroism spectra plus spectrophotometric titration of tyrosine residues lend additional support to this hypothesis. 相似文献
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E. Werner P. Roth U. Heinrichs A. Giussani M. C. Cantone Th. Zilker 《Isotopes in environmental and health studies》2013,49(2):123-132
Abstract Although molybdenum is considered to be an essential trace metal for humans, the knowledge about its metabolism is rather limited. The present study was aimed at the assessment of biokinetics following intravenous injection of trace amounts of 95Mo or 96Mo into five healthy volunteers. In a total of 11 investigations, the plasma clearance up to eight hours and the urinary excretion for at least three days after the injection were evaluated. The tracer concentrations were determined by proton nuclear activation analysis in blood plasma and by thermal ionization mass spectrometry in urine samples respectively. In all subjects, the plasma clearance is much faster than expected from the literature. The data obtained for the plasma clearance of the tracer can reasonably be fitted by a two exponential equation. The half times of the fast component range between 4 and 70 minutes and for the slow component between 3 and 30 hours. The urinary excretion of the injected tracer seems also to be faster than expected and the fractions lost are higher for larger doses administered. For the smallest dose given, 34% of the injected tracer were excreted within one day whereas for the four times larger dose about 60% were lost. These findings on urinary excretion are in agreement with recently published results. 相似文献
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Karcher Wolfgang Roth Stefan Spodarev Evgeny Walk Corinna 《Statistical Inference for Stochastic Processes》2019,22(2):263-306
Statistical Inference for Stochastic Processes - Given a low frequency sample of an infinitely divisible moving average random field $$\{\int _{\mathbb {R}^d} f(x-t)\varLambda (dx); \ t \in \mathbb... 相似文献