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61.
[reaction: see text] A straightforward and highly efficient synthesis of aromatic azides from the corresponding amines is accomplished using triflyl azide under mild conditions. 相似文献
62.
The title subject has been studied through galvanostatic single-pulse and chronopotentiometric measurements on the Mn(Hg)/Mn(II) electrode and equilibrium measurements on the same and the Ag/AgCl electrode, all in x MMnCl2+(0.5?x)M MgCl2 solutions of pH 4.3–4.9 at 25°C. The Mn(Hg)/Mn(II) reactions are found to occur in two consecutive steps, an unsymmetric (αc near 0.8) ion-transfer step Mn(Hg)/Mn(I) and an essentially symmetric (αc near 0.5) electron-transfer step Mn(I)/Mn(II). Besides charge transfer, no sluggishness other than diffusion is observed, but the dispersed precipitate Mn2Hg5 of saturated amalgam serves as an ageing-dependent source of anodic reactant Mn(Hg). Quantitative kinetic and thermodynamic data are presented and discussed. Comparisons are made to corresponding reactions for the succeeding elements iron, cobalt, nickel, copper, and zinc. 相似文献
63.
Fredrik Bergstr?m Ilya Mikhalyov Peter H?ggl?f Rüdiger Wortmann Tor Ny Lennart B A Johansson 《Journal of the American Chemical Society》2002,124(2):196-204
A ground-state dimer (denoted D(I)) exhibiting a strong absorption maximum at 477 nm (epsilon = 97 000 M(-1)cm(-1)) can form between adjacent BODIPY groups attached to mutant forms of the protein, plasminogen activator inhibitor type 1 (PAI-1). No fluorescence from excited D(I) was detected. A locally high concentration of BODIPY groups was also achieved by doping lipid phases (micelles, vesicles) with BODIPY-labeled lipids. In addition to an absorption band located at about 480 nm, a new weak absorption band is also observed at ca. 570 nm. Both bands are ascribed to the formation of BODIPY dimers of different conformation (D(I) and D(II)). Contrary to D(I) in PAI-1, the D(II) aggregates absorbing at 570 nm are emitting light observed as a broad band centered at about 630 nm. The integrated absorption band of D(I) is about twice that of the monomer, which is compatible with exciton coupling within a dimer. The F?rster radius of electronic energy transfer between a BODIPY excited monomer and the ground-state dimer (D(I)()) is 57 +/- 2 A. A simple model of exciton coupling suggests that in D(I) two BODIPY groups are stacked on top of each other in a sandwich-like configuration with parallel electronic transition dipoles. For D(II) the model suggests that the S(0) --> S(1) transition dipoles are colinear. An explanation for the previously reported (J. Am. Chem. Soc. 1994, 116, 7801) exceptional light spectroscopic properties of BODIPY is also presented. These are ascribed to the extraordinary electric properties of the BODIPY chromophore. First, changes of the permanent electric dipole moment (Delta(mu) approximately -0.05 D) and polarizability (-26 x 10(-40) C m(2) V(-1)) between the ground and the first excited states are small. Second, the S(0) <--> S(1) electronic transition dipole moments are perpendicular to Delta(mu). 相似文献
64.
Hima S. Joshi Ramin Jamshidi Yitzhak Tor 《Angewandte Chemie (International ed. in English)》1999,38(18):2721-2725
Multiple emission colors can be generated with the same compound from a novel family of highly emissive and visibly fluorescent 1,10-phenanthrolines 1 . The emission wavelength of any derivative is dictated by the nature of its substituent and can be further modulated by exogenous additives such as protons or metal ions. R=H, Me, OMe, NMe2. 相似文献
65.
66.
Complete geometry optimizations using ab initio SCF/3-21G* calculations were performed on silatrane and azasilatrane, on their fluoro derivatives, and on methylsilatrane. By comparison with optimized geometries obtained for a series of model systems, the predicted transannular internuclear distances were interpreted in terms of the combined effects of electronegative substituents on Si and the anomeric interaction in the silatranes. The predicted geometries indicate that there is a weak transannular interaction in silatrane and a more significant one in azasilatrane, the predicted equilibrium distances being 2.66 and 2.15 Å, respectively. © 1996 John Wiley & Sons, Inc. 相似文献
67.
Let ω be a primitive element of GF(2n), where . Let d=(22k+2s+1-2k+1-1)/(2s-1), where n=2k, and s is such that 2s divides k. We prove that the binary m-sequences s(t)=tr(ωt) and s(dt) have a four-level cross-correlation function and give the distribution of the values. 相似文献
68.
Aminoglycosides (including neomycin B and tobramycin) exhibit poor uptake by eukaryotic cell lines. When the amines of these natural products are converted into guanidine groups, their cellular uptake is dramatically enhanced. We have synthesized BODIPY-containing aminoglycosides and guanidinoglycosides to evaluate their cellular uptake properties. Fluorescence activated cell sorting (FACS) and fluorescence microscopy are used to compare the membrane translocation and the cellular localization of these compounds. Upon guanidinylation, the cellular uptake efficiencies of tobramycin and neomycin B are enhanced by 10-fold and 20-fold, respectively. Guanidino-neomycin B exhibits a highly efficient uptake, superior to a fluorescent poly-arginine peptide. Interestingly, the cellular uptake of this common transduction peptide is inhibited by guanidine-neomycin B, suggesting a similar uptake mechanism for both the arginine-rich peptides and the guanidinoglycosides. 相似文献
69.
Synthesis and anti-HIV activity of guanidinoglycosides 总被引:6,自引:0,他引:6
The new guanidinylation reagent N,N'-diBoc-N'-triflylguanidine was used to efficiently convert multiamine-containing glycosides including kanamycin A and B, tobramycin, paromomycin, and neomycin B to the corresponding fully guanidinylated analogues (guanidinoglycosides). This transformation occurs in the presence of H(2)O under mild conditions. Guanidinotobramycin and guanidinoneomycin B were found to inhibit the replication of the HIV virus with activities approximately 100 times greater than the parent aminoglycosides. 相似文献
70.