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Roy RS Gopi HN Raghothama S Karle IL Balaram P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(12):3295-3302
The effects of inserting unsubstituted omega-amino acids into the strand segments of model beta-hairpin peptides was investigated by using four synthetic decapeptides, Boc-Leu-Val-Xxx-Val-D-Pro-Gly-Leu-Xxx-Val-Val-OMe: peptide 1 (Xxx=Gly), peptide 2 (Xxx=betaGly=betahGly=homoglycine, beta-glycine), peptide 3 (Xxx=gammaAbu=gamma-aminobutyric acid), peptide 4 (Xxx=deltaAva=delta-aminovaleric acid). 1H NMR studies (500 MHz, methanol) reveal several critical cross-strand NOEs, providing evidence for beta-hairpin conformations in peptides 2-4. In peptide 3, the NMR results support the formation of the nucleating turn, however, evidence for cross-strand registry is not detected. Single-crystal X-ray diffraction studies of peptide 3 reveal a beta-hairpin conformation for both molecules in the crystallographic asymmetric unit, stabilized by four cross-strand hydrogen bonds, with the gammaAbu residues accommodated within the strands. The D-Pro-Gly segment in both molecules (A,B) adopts a type II' beta-turn conformation. The circular dichroism spectrum for peptide 3 is characterized by a negative CD band at 229 nm, whereas for peptides 2 and 4, the negative band is centered at 225 nm, suggesting a correlation between the orientation of the amide units in the strand segments and the observed CD pattern. 相似文献
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Gersen H Karle TJ Engelen RJ Bogaerts W Korterik JP van Hulst NF Krauss TF Kuipers L 《Physical review letters》2005,94(12):123901
The eigenfield distribution and the band structure of a photonic crystal waveguide have been measured with a phase-sensitive near-field scanning optical microscope. Bloch modes, which consist of more than one spatial frequency, are visualized in the waveguide. In the band structure, multiple Brillouin zones due to zone folding are observed, in which positive and negative dispersion is seen. The negative slopes are shown to correspond to a negative phase velocity but a positive group velocity. The lateral mode profile for modes separated by one reciprocal lattice vector is found to be different. 相似文献
80.
Jean M. Karle Apurba K. Bhattacharjee Jonathan L. Vennerstrom 《Journal of chemical crystallography》2002,32(5-6):133-139
The neighboring 4-aminoquinoline substituents of the bisquinoline (±)-trans-N
1,N
2-bis(7-chloroquinolin-4-yl)cyclohexane-1,2-diamine dimethanesulfonate salt crystallized in the diequatorial position which is in agreement with quantum chemical calculations. The bisquinoline salt crystallized in the monoclinic C2/c space group with a = 19.328(4) Å, b = 15.618(3) Å, c = 20.382(4) Å, = 98.84(3)°. The two quinoline nitrogen atoms are protonated by the salt as predicted by calculated electrostatic surface potentials. The –5 kcal/mol isopotential surface of the bisquinoline resembles that of chloroquine, which may explain the potent inhibition of hematin polymerization by both the bisquinoline and chloroquine. The smaller HOMO/LUMO gap of the bisquinoline is consistent with its phototoxicity. The overall conformation, the ability of all nitrogen atoms to participate in hydrogen bonding, and the electrostatic interaction of the quinoline rings in the crystal packing may all aid in the determination of the binding pharmacophore of the bisquinoline. 相似文献