共查询到20条相似文献，搜索用时 15 毫秒
1.
Direct observation of the femtosecond excited-state cis-trans isomerization in bacteriorhodopsin 总被引：12，自引：0，他引：12
Femtosecond optical measurement techniques have been used to study the primary photoprocesses in the light-driven transmembrane proton pump bacteriorhodopsin. Light-adapted bacteriorhodopsin was excited with a 60-femtosecond pump pulse at 618 nanometers, and the transient absorption spectra from 560 to 710 nanometers were recorded from -50 to 1000 femtoseconds by means of 6-femtosecond probe pulses. By 60 femtoseconds, a broad transient hole appeared in the absorption spectrum whose amplitude remained constant for about 200 femtoseconds. Stimulated emission in the 660- to 710-nanometer region and excited-state absorption in the 560- to 580-nanometer region appeared promptly and then shifted and decayed from 0 to approximately 150 femtoseconds. These spectral features provide a direct observation of the 13-trans to 13-cis torsional isomerization of the retinal chromophore on the excited-state potential surface. Absorption due to the primary ground-state photoproduct J appears with a time constant of approximately 500 femtoseconds. 相似文献
2.
Kukura P McCamant DW Yoon S Wandschneider DB Mathies RA 《Science (New York, N.Y.)》2005,310(5750):1006-1009
The primary event that initiates vision is the light-induced 11-cis to all-trans isomerization of retinal in the visual pigment rhodopsin. Despite decades of study with the traditional tools of chemical reaction dynamics, both the timing and nature of the atomic motions that lead to photoproduct production remain unknown. We used femtosecond-stimulated Raman spectroscopy to obtain time-resolved vibrational spectra of the molecular structures formed along the reaction coordinate. The spectral evolution of the vibrational features from 200 femtoseconds to 1 picosecond after photon absorption reveals the temporal sequencing of the geometric changes in the retinal backbone that activate this receptor. 相似文献
3.
Bragg AE Verlet JR Kammrath A Cheshnovsky O Neumark DM 《Science (New York, N.Y.)》2004,306(5696):669-671
The electronic relaxation dynamics of size-selected (H2O)n-/(D2O)n[25 eaq-(s(dagger)) internal conversion lifetime. 相似文献
4.
Effect of carboxylic acid side chains on the absorption maximum of visual pigments 总被引：21，自引：0，他引：21
The proposal that the absorption maximum of the visual pigments is governed by interaction of the 11-cis-retinal chromophore with charged carboxylic acid side chains in the membrane-embedded regions of the proteins has been tested by mutating five Asp and Glu residues thought to be buried in rhodopsin. Changing Glu113 to Gln causes a dramatic shift in the absorption maximum from 500 nanometers to 380 nanometers, a decrease in the pKa (acidity constant) of the protonated Schiff base of the chromophore to about 6, and a greatly increased reactivity with hydroxylamine. Thus Glu113 appears to be the counterion to the protonated Schiff base. Wavelength modulation in visual pigments apparently is not governed by electrostatic interaction with carboxylate residues, other than the counterion. 相似文献
5.
Bernard GD 《Science (New York, N.Y.)》1979,203(4385):1125-1127
Noninvasive photochemical and physiological experiments with intact butterflies of 17 species showed that nine species have a rhodopsin absorbing maximally at 610 nanometers, contained in retinular cells that are maximally sensitive at 610 nanometers. This is the longest-wavelength visual pigment known for an invertebrate. Eight species of butterflies lack the 610-nanometers rhodopsin. All species possess a rhodopsin absorbing maximally in the green region of the spectrum. 相似文献
6.
Schoenlein RW Chattopadhyay S Chong HH Glover TE Heimann PA Shank CV Zholents AA Zolotorev MS 《Science (New York, N.Y.)》2000,287(5461):2237-2240
Femtosecond synchrotron pulses were generated directly from an electron storage ring. An ultrashort laser pulse was used to modulate the energy of electrons within a 100-femtosecond slice of the stored 30-picosecond electron bunch. The energy-modulated electrons were spatially separated from the long bunch and used to generate approximately 300-femtosecond synchrotron pulses at a bend-magnet beamline, with a spectral range from infrared to x-ray wavelengths. The same technique can be used to generate approximately 100-femtosecond x-ray pulses of substantially higher flux and brightness with an undulator. Such synchrotron-based femtosecond x-ray sources offer the possibility of applying x-ray techniques on an ultrafast time scale to investigate structural dynamics in condensed matter. 相似文献
7.
Schenkl S van Mourik F van der Zwan G Haacke S Chergui M 《Science (New York, N.Y.)》2005,309(5736):917-920
The ultrafast evolution of the electric field within bacteriorhodopsin was measured by monitoring the absorption changes of a tryptophan residue after excitation of retinal. The Trp absorption decreases within the first 200 femtoseconds and then recovers on time scales typical for retinal isomerization and vibrational relaxation. A model of excitonic coupling between retinal and tryptophans shows that the signal reflects a gradual rise of the retinal difference dipole moment, which precedes and probably drives isomerization. The results suggest an intimate connection between the progressive dipole moment change and the retinal skeletal changes reported over the same time scale. 相似文献
8.
Spectral tuning of pigments underlying red-green color vision 总被引：18，自引：0，他引：18
Variations in the absorption spectra of cone photopigments over the spectral range of about 530 to 562 nanometers are a principal cause of individual differences in human color vision and of differences in color vision within and across other primates. To study the molecular basis of these variations, nucleotide sequences were determined for eight primate photopigment genes. The spectral peaks of the pigments specified by these genes spanned the range from 530 to 562 nanometers. Comparisons of the deduced amino acid sequences of these eight pigments suggest that three amino acid substitutions produce the approximately 30-nanometer difference in spectral peaks of the pigments underlying human red-green color vision, and red shifts of specific magnitudes are produced by replacement of nonpolar with hydroxyl-bearing amino acids at each of the three critical positions. 相似文献
9.
Steinmeyer G Sutter DH Gallmann L Matuschek N Keller U 《Science (New York, N.Y.)》1999,286(5444):1507-1512
Optical pulses in the 5-femtosecond range are produced by a variety of methods. Although different in technical detail, each method relies on the same three key components: spectral broadening due to the nonlinear optical Kerr effect, dispersion control, and ultrabroadband amplification. The state of the art of ultrashort pulse generation is reviewed with a focus on direct laser oscillator schemes. 相似文献
10.
Drescher M Hentschel M Kienberger R Tempea G Spielmann C Reider GA Corkum PB Krausz F 《Science (New York, N.Y.)》2001,291(5510):1923-1927
Single soft-x-ray pulses of approximately 90-electron volt (eV) photon energy are produced by high-order harmonic generation with 7-femtosecond (fs), 770-nanometer (1.6 eV) laser pulses and are characterized by photoionizing krypton in the presence of the driver laser pulse. By detecting photoelectrons ejected perpendicularly to the laser polarization, broadening of the photoelectron spectrum due to absorption and emission of laser photons is suppressed, permitting the observation of a laser-induced downshift of the energy spectrum with sub-laser-cycle resolution in a cross correlation measurement. We measure isolated x-ray pulses of 1.8 (+0.7/-1.2) fs in duration, which are shorter than the oscillation cycle of the driving laser light (2.6 fs). Our techniques for generation and measurement offer sub-femtosecond resolution over a wide range of x-ray wavelengths, paving the way to experimental attosecond science. Tracing atomic processes evolving faster than the exciting light field is within reach. 相似文献
11.
The vibrational dynamics of the retinal chromophore all-trans-to-13-cis photoisomerization in bacteriorhodopsin has been studied with mid-infrared absorption spectroscopy at high time resolution (about 200 femtoseconds). After photoexcitation of light-adapted bacteriorhodopsin, the transient infrared absorption was probed in a broad spectral region, including vibrations with dominant C-C, C=C, and C=NH stretching mode amplitude. All photoproduct modes, especially those around 1190 reciprocal-centimeters that are indicative for a 13-cis configuration of the chromophore, rise with a time constant of approximately 0.5 picosecond. The results presented give direct vibrational-spectroscopic evidence for the isomerization taking place within 0.5 picosecond, as has been suggested by previous optical femtosecond time-resolved experiments but questioned recently by picosecond time-resolved vibrational spectroscopy experiments. 相似文献
12.
The laser-induced movement of CO molecules over a platinum surface was followed in real time by means of ultrafast vibrational spectroscopy. Because the CO molecules bound on different surface sites exhibit different C-O stretch vibrational frequencies, the site-to-site hopping, triggered by excitation with a laser pulse, can be determined from subpicosecond changes in the vibrational spectra. The unexpectedly fast motion--characterized by a 500-femtosecond time constant--reveals that a rotational motion of the CO molecules, rather than pure translation, is required for this diffusion process. This conclusion is corroborated by density functional theory calculations. 相似文献
13.
McClintock WE Izenberg NR Holsclaw GM Blewett DT Domingue DL Head JW Helbert J McCoy TJ Murchie SL Robinson MS Solomon SC Sprague AL Vilas F 《Science (New York, N.Y.)》2008,321(5885):62-65
During MESSENGER's first flyby of Mercury, the Mercury Atmospheric and Surface Composition Spectrometer made simultaneous mid-ultraviolet to near-infrared (wavelengths of 200 to 1300 nanometers) reflectance observations of the surface. An ultraviolet absorption (<280 nanometers) suggests that the ferrous oxide (Fe2+) content of silicates in average surface material is low (less than 2 to 3 weight percent). This result is supported by the lack of a detectable 1-micrometer Fe2+ absorption band in high-spatial-resolution spectra of mature surface materials as well as immature crater ejecta, which suggests that the ferrous iron content may be low both on the surface and at depth. Differences in absorption features and slope among the spectra are evidence for variations in composition and regolith maturation of Mercury's surface. 相似文献
14.
Human rhodopsin in aqueous solution has lambda(max). of 493 mmicro and is lower in the spectrum than the rhodopsins of all other known vertebrates, with the exception of certain deep-sea fishes. Its molar extinction is 40,000 +/- 800. Like other rhodopsins, it bleaches to a mixture of opsin and all-trans retinene and is resynthesized by incubating opsin with neo-b (11-cis) retinene. The regenerated rhodopsin has the same lambda(max). as the extracted pigment; this is due, therefore, not to an unusual retinene but to a characteristic human opsin. The regeneration in solution from opsin and neo-b retinene is a second-order reaction with a half-time, at 29.5 degrees C, of about 2.5 minutes. This is much faster than the synthesis of rhodopsin in the living human eye, and faster than human rod dark-adaptation; the rate of both processes in vivo must be limited by reactions which precede the union of neo-b retinene with opsin, the final step in rhodopsin synthesis. In the rods, rhodopsin is virtually in the solid state-highly oriented in close relation with other highly oriented molecules. In this situation its spectrum is displaced toward the red (lambda(max) 500 mmicro) and is narrower than in solution. For light entering the rods axially, rhodopsin has also a considerably increased extinction, some 1.5 times higher than when randomly oriented. The spectrum of rhodopsin in rods agrees well in form and position with the spectral sensitivity of human rod vision, measured at the retinal surface. 相似文献
15.
Rhodopsin mutants that bind but fail to activate transducin 总被引：19，自引：0，他引：19
R R Franke B K?nig T P Sakmar H G Khorana K P Hofmann 《Science (New York, N.Y.)》1990,250(4977):123-125
Rhodopsin is a member of a family of receptors that contain seven transmembrane helices and are coupled to G proteins. The nature of the interactions between rhodopsin mutants and the G protein, transduction (Gt), was investigated by flash photolysis in order to monitor directly Gt binding and dissociation. Three mutant opsins with alterations in their cytoplasmic loops bound 11-cis-retinal to yield pigments with native rhodopsin absorption spectra, but they failed to stimulate the guanosine triphosphatase activity of Gt. The opsin mutations included reversal of a charged pair conserved in all G protein-coupled receptors at the cytoplasmic border of the third transmembrane helix (mutant CD1), replacement of 13 amino acids in the second cytoplasmic loop (mutant CD2), and deletion of 13 amino acids from the third cytoplasmic loop (mutant EF1). Whereas mutant CD1 failed to bind Gt, mutants CD2 and EF1 showed normal Gt binding but failed to release Gt in the presence of guanosine triphosphate. Therefore, it appears that at least the second and third cytoplasmic loops of rhodopsin are required for activation of bound Gt. 相似文献
16.
The photochemistry of poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-p-phenylene-vinylene] (MEH-PPV) has been found to be highly dependent on the presence of O(2), which increases singlet exciton quenching dramatically. Spectroscopy on isolated single molecules of MEH-PPV in polycarbonate films that exclude O(2) reveals two distinct polymer conformations with fluorescence maxima near 555 and 580 nanometers wavelength, respectively. Time-resolved single-molecule data demonstrate that the 580-nanometer conformation exhibits a "landscape" for intramolecular electronic energy relaxation with a "funnel" that contains a 580-nanometer singlet exciton trap at the bottom. The exciton traps can be converted to exciton quenchers by reaction with O(2). Conformationally induced, directed-energy transfer is arguably a critical dynamical process that is responsible for many of the distinctive photophysical properties of conjugated polymers. 相似文献
17.
Shelton RK Ma LS Kapteyn HC Murnane MM Hall JL Ye J 《Science (New York, N.Y.)》2001,293(5533):1286-1289
We generated a coherently synthesized optical pulse from two independent mode-locked femtosecond lasers, providing a route to extend the coherent bandwidth available for ultrafast science. The two separate lasers (one centered at 760 nanometers wavelength, the other at 810 nanometers) are tightly synchronized and phase-locked. Coherence between the two lasers is demonstrated via spectral interferometry and second-order field cross-correlation. Measurements reveal a coherently synthesized pulse that has a temporally narrower second-order autocorrelation width and that exhibits a larger amplitude than the individual laser outputs. This work represents a new and flexible approach to the synthesis of coherent light. 相似文献
18.
Prolonged exposure of rhesus monkeys to intense blue light produces long-term changes which are consistent with loss of response of those cones that contain a photopigment with peak absorption at 445 nanometers. The 90 percent reduction of spectral sensitivity in the blue region has lasted more than 5 months. Reduced sensitivity to long wavelengths is produced by adaptation to light of 520 nanometers. This reduced sensitivity, which lasts no more than 30 days, is attributed to a temporary loss of response of the cones containing a photopigment with peak absorption at 535 nanometers. 相似文献
19.
Transducin activation by rhodopsin without a covalent bond to the 11-cis-retinal chromophore 总被引：3，自引：0，他引：3
Rhodopsin and the visual pigments are a distinct group within the family of G-protein-linked receptors in that they have a covalently bound ligand, the 11-cis-retinal chromophore, whereas all of the other receptors bind their agonists through noncovalent interactions. The retinal chromophore in rhodopsin is bound by means of a protonated Schiff base linkage to the epsilon-amino group of Lys-296. Two rhodopsin mutants have been constructed, K296G and K296A, in which the covalent linkage to the chromophore is removed. Both mutants form a pigment with an absorption spectrum close to that of the wild type when reconstituted with the Schiff base of an n-alkylamine and 11-cis-retinal. In addition, the pigment formed from K296G and the n-propylamine Schiff base of 11-cis-retinal was found to activate transducin in a light-dependent manner, with 30 to 40% of the specific activity measured for the wild-type protein. It appears that the covalent bond is not essential for binding of the chromophore or for catalytic activation of transducin. 相似文献
20.
Chopra NG Luyken RJ Cherrey K Crespi VH Cohen ML Louie SG Zettl A 《Science (New York, N.Y.)》1995,269(5226):966-967
The successful synthesis of pure boron nitride (BN) nanotubes is reported here. Multi-walled tubes with inner diameters on the order of 1 to 3 nanometers and with lengths up to 200 nanometers were produced in a carbon-free plasma discharge between a BN-packed tungsten rod and a cooled copper electrode. Electron energy-loss spectroscopy on individual tubes yielded B:N ratios of approximately 1, which is consistent with theoretical predictions of stable BN tube structures. 相似文献