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81.
Saxon E Luchansky SJ Hang HC Yu C Lee SC Bertozzi CR 《Journal of the American Chemical Society》2002,124(50):14893-14902
The structure of sialic acid on living cells can be modulated by metabolism of unnatural biosynthetic precursors. Here we investigate the conversion of a panel of azide-functionalized mannosamine and glucosamine derivatives into cell-surface sialosides. A key tool in this study is the Staudinger ligation, a highly selective reaction between modified triarylphosphines and azides that produces an amide-linked product. A preliminary study of the mechanism of this reaction, and refined conditions for its in vivo execution, are reported. The reaction provided a means to label the glycoconjugate-bound azidosugars with biochemical probes. Finally, we demonstrate that the cell-surface Staudinger ligation is compatible with hydrazone formation from metabolically introduced ketones. These two strategies provide a means to selectively modify cell-surface glycans with exogenous probes. 相似文献
82.
Density Functional Theory (DFT) has been applied to characterize the early stages of the reaction of dioxygenation of [(triphos)M(catecholate)]+ complexes [M = Co(III), Ir(III); triphos = MeC(CH2PPh2)3], which have been considered to be models of ring-opening dioxygenases. The structural features of the starting complexes and of the intermediate complexes formed by addition of O2 to the coordinated catecholato ion are well reproduced. The calculations showed that this preliminary stage can be obtained only when the oxygen molecule attacks the molecule on the catecholato site. 相似文献
83.
84.
Carolyn E. M. Morris A. E. Alexander A. G. Parts 《Journal of polymer science. Part A, Polymer chemistry》1966,4(5):985-995
The polymerization of methyl acrylate in water and in dilute, aqueous, soap solutions, initiated by potassium peroxydisulfate, has been investigated, a dilatometric method being used to follow the conversion. It has been shown that small amounts of an anionic soap increase the rate of reaction while a cationic soap has the reverse effect. The change of molecular weight with conversion has also been examined as well as the effect of the exclusion of oxygen from the system. 相似文献
85.
86.
The inhomogeneous master equation obtained in a previous paper (by Van Vliet) is employed to obtain as first-moment equation two quantum mechanical Boltzmann equations (diagonal) for systems of weakly interacting identical particles. The interactions considered are of a binary nature: fermion-fermion or boson-boson. The resulting equations have the same structure as before. The total Boltzmann equation (diagonal and nondiagonal part) is also derived. 相似文献
87.
Temporary threshold shift in bottlenose dolphins (Tursiops truncatus) exposed to mid-frequency tones
Finneran JJ Carder DA Schlundt CE Ridgway SH 《The Journal of the Acoustical Society of America》2005,118(4):2696-2705
A behavioral response paradigm was used to measure hearing thresholds in bottlenose dolphins before and after exposure to 3 kHz tones with sound exposure levels (SELs) from 100 to 203 dB re 1 microPa2 s. Experiments were conducted in a relatively quiet pool with ambient noise levels below 55 dB re 1 microPa2/Hz at frequencies above 1 kHz. Experiments 1 and 2 featured 1-s exposures with hearing tested at 4.5 and 3 kHz, respectively. Experiment 3 featured 2-, 4-, and 8-s exposures with hearing tested at 4.5 kHz. For experiment 2, there were no significant differences between control and exposure sessions. For experiments 1 and 3, exposures with SEL=197 dB re 1 microPa2 s and SEL > or = 195 dB re 1 microPa2 s, respectively, resulted in significantly higher TTS4 than control sessions. For experiment 3 at SEL= 195 dB re 1 microPa2 s, the mean TTS4 was 2.8 dB. These data are consistent with prior studies of TTS in dolphins exposed to pure tones and octave band noise and suggest that a SEL of 195 dB re 1 microPa2 s is a reasonable threshold for the onset of TTS in dolphins and white whales exposed to midfrequency tones. 相似文献
88.
89.
We consider smooth multimodal maps which have finitely many non-flat critical points. We prove the existence of real bounds. From this we obtain a new proof for the non-existence of wandering intervals, derive extremely useful improved Koebe principles, show that high iterates have `negative Schwarzian derivative' and give results on ergodic properties of the map. One of the main complications in the proofs is that we allow to have inflection points.
90.
The dispersion curves of the dielectric response in single crystal NH4H2PO4 were obtained in the radio frequency range and below the high-temperature transition at Tp−160 °C. The results reveal dielectric relaxation at low frequency, which is about 105 Hz at 70 °C, and it shifts to higher frequencies (∼3×106 Hz) as the temperature increases. The relaxation frequency was determined from the peak obtained in the imaginary part of the permittivity as well as from the derivative of the real part of the permittivity. The activation energy Ea=0.55 eV, obtained from the relaxation frequency is very close to that derived from the dc conductivity. We suggest that this dielectric relaxation could be due to the proton jump and phosphate reorientation that cause distortion and change the local lattice polarizability inducing dipoles like 相似文献