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141.
Sahoo H Roccatano D Hennig A Nau WM 《Journal of the American Chemical Society》2007,129(31):9762-9772
Fluorescence resonance energy transfer (FRET) from the amino acid tryptophan (Trp) as donor and a 2,3-diazabicyclo[2.2.2]oct-2-ene-labeled asparagine (Dbo) as acceptor in peptides of the general structure Trp-(Pro)n-Dbo-NH2 (n = 1-6) was investigated by steady-state and time-resolved fluorescence, CD, and NMR spectroscopy as well as by molecular dynamics (MD) simulations (GROMOS96 force field). The Trp/Dbo FRET pair is characterized by a very short F?rster radius (R0 ca. 9 A), which allowed distance determinations in such short peptides. Water and propylene glycol were investigated as solvents. The peptides were designed to show an early nucleation of the poly(Pro)II (PPII) secondary helix structure for n > or = 2, which was confirmed by their CD spectra. The shortest peptide (n = 1) adopts preferentially the trans conformation about the Trp-Pro bond, as confirmed by NMR spectra. The FRET efficiencies ranged 2-72% and were found to depend sensitively on the peptide length, i.e., the number of intervening proline residues. The analysis of the FRET data at different levels of theory (assuming either a fixed distance or distance distributions according to a wormlike chain or Gaussian model) afforded donor-acceptor distances between ca. 8 A (n = 1) and ca. 16 A (n = 6) in water, which were found to be similar or slightly higher in propylene glycol. The distances afforded by the Trp/Dbo FRET pair were found to be reasonable in comparison to literature data, expectations from the PPII helix structure, and the results from MD simulations. The persistence lengths for the longer peptides were found to lie at 30-70 A in water and 220 +/- 40 A in propylene glycol, suggesting a more rigid PPII helical structure in propylene glycol. A detailed comparison with literature data on FRET in polyprolines demonstrates that the donor-acceptor distances extracted by FRET are correlated with the F?rster radii of the employed FRET pairs. This demonstrates the limitations of using FRET as a spectroscopic ruler for short polyprolines, which is presumably due to the breakdown of the point dipole approximation in F?rster theory, when the size of the chromophores becomes comparable or larger than the distances under investigation. 相似文献
142.
In order to apply ab initio wave-function-based correlation methods to metals, it is desirable to split the calculation into a mean-field part and a correlation part. Whereas the mean-field part (here Hartree-Fock) is performed in the extended periodic system, it is necessary to use for the correlation part local wave-function-based correlation methods in finite fragments of the solid. For these finite entities it is necessary to construct an embedding. The authors suggest an embedding scheme which has itself no metallic character but can mimic the metal in the internal region, where the atoms are correlated. With this embedding it is also possible to localize the metallic orbitals in the central part. The long-range nonadditive contributions of metallicity and correlation are treated with the method of increments. In this paper they present different ways to construct such an embedding and discuss the influence of the embedding on the correlation energy of the solid. 相似文献
143.
Cho SJ Maysinger D Jain M Röder B Hackbarth S Winnik FM 《Langmuir : the ACS journal of surfaces and colloids》2007,23(4):1974-1980
Several studies suggested that the cytotoxic effects of quantum dots (QDs) may be mediated by cadmium ions (Cd2+) released from the QDs cores. The objective of this work was to assess the intracellular Cd2+ concentration in human breast cancer MCF-7 cells treated with cadmium telluride (CdTe) and core/shell cadmium selenide/zinc sulfide (CdSe/ZnS) nanoparticles capped with mercaptopropionic acid (MPA), cysteamine (Cys), or N-acetylcysteine (NAC) conjugated to cysteamine. The Cd2+ concentration determined by a Cd2+-specific cellular assay was below the assay detection limit (<5 nM) in cells treated with CdSe/ZnS QDs, while in cells incubated with CdTe QDs, it ranged from approximately 30 to 150 nM, depending on the capping molecule. A cell viability assay revealed that CdSe/ZnS QDs were nontoxic, whereas the CdTe QDs were cytotoxic. However, for the various CdTe QD samples, there was no dose-dependent correlation between cell viability and intracellular [Cd2+], implying that their cytotoxicity cannot be attributed solely to the toxic effect of free Cd2+. Confocal laser scanning microscopy of CdTe QDs-treated cells imaged with organelle-specific dyes revealed significant lysosomal damage attributable to the presence of Cd2+ and of reactive oxygen species (ROS), which can be formed via Cd2+-specific cellular pathways and/or via CdTe-triggered photoxidative processes involving singlet oxygen or electron transfer from excited QDs to oxygen. In summary, CdTe QDs induce cell death via mechanisms involving both Cd2+ and ROS accompanied by lysosomal enlargement and intracellular redistribution. 相似文献
144.
145.
Cotton fabric is modified by means of polycarboxylic acids in combination with an inorganic or an organic catalyst in order
to impart durable press properties. After the curing process the cellulosic specimen is washed off to remove both the portion
of the polycarboxylic acid that has not reacted and the catalyst applied. The treated cellulosic fabric is saponified with
a sodium hydroxide solution to extract the PCA that has reacted with the cellulosic material. Both the wash liquor and the
saponification liquor are investigated by means of isocratic HPLC using Aminex HPX-87-H as stationary phase. Excellent separation
of the various polycarboxylic acids that are applied as crosslinking agents or as organic catalysts is achieved. The HPLC
method presented enables the identification and quantification of the polycarboxylic acids.
Received: 19 January 1999 / Revised: 24 March 1999 / Accepted: 28 March 1999 相似文献
146.
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148.
Rubidium Decaamidodichromate(III), Rb4Cr2(NH2)10 – Synthesis and Crystal Structure The reaction of chromium(III) with rubidium amide in a molar ratio of Cr(NH2)3/RbNH2 = 1 : 1.75 at 140 °C and p(NH3) = 3 kbar in a high-pressure autoclave results after 90 days in dark violet crystals of Rb4Cr2(NH2)10. Structure determination was done by single crystal X-ray methods:Pna21 (No. 33), Z = 4, a = 12.244(3) Å, b = 6.727(1) Å, c = 19.775(5) Å, N(F2o > 3σ(F2o)) = 1046, N(Var.) = 94, R/Rw = 0,051/0,059TAB;The structure of Rb4Cr2(NH2)10 contains isolated, face-sharing N-octahedra around two Cr3+-ions giving [Cr(NH2)3(NH2)3/2]23–. These are arranged to oneanother following the motif of a hexagonal closest packing. They are connected via Rb+- and one further amide ion not bound to Cr3+. The compound is characterized by thermoanalytical and IR-/Raman-spectroscopic measurements. 相似文献
149.
Diphenyl-o-silaborane ( 1 ) can be obtained by sublimation as colourless crystalline material in a yield of 23%. The disilaborane 1 was characterized by NMR spectroscopy, mass spectrometry and X-ray structure analysis. The neutral closo cluster 1 reacts with [Zr(NMe2)4] or [Ta(NMe2)5] to give the dimethylamide adduct [(Me2N)(PhSi)2B10H10]– of the disilaborane. 相似文献
150.