Vibrational analysis of the all-trans retinal protonated Schiff base

Smith, Steven O.; Myers, Anne B.; Mathies, R. A.; Pardoen, J. A.; Winkel, C.; Berg, E. M. M. Van Den; Lugtenburg, J.

doi:10.1016/s0006-3495(85)83961-8

Cited by 120 publications

(127 citation statements)

References 25 publications

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“…The conjugation subsequently dies off on moving towards the cyclohexene ring end of the molecule. Experimental results (29) show an increase in the frequency of the C14-C15 stretch on protonation of the Schiff base, which is in agreement with the above results. The bond order of the Cll-C12 double bond is reduced considerably on protonation of the Schiff base thereby facilitating the rotation of the C1 1-C12 double bond or in other words facilitates the cis-trans isomerization (c. f. Fig.…”

Section: It Is Evident Fromsupporting

confidence: 90%

Effect of protonation on the ground state properties of retinal analogs: an ab-initio study

Poirier¹,

Yadav²,

Śurján³

1987

Can. J. Chem.

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. Can. J. Chem. 65, 892 (1987). The ground state properties (bond lengths, bond orders, net atomic charge distribution) of various cis and trans isomers of retinal analogs have been studied at ab initio SCF and correlated levels. The effect of protonation on the properties of the retinal Schiff base analogs has also been studied. Convergence in various properties has been observed with increasing chain length justifying the use of smaller analogs mimicking retinal. Convergence is, however, slower for the protonated retinal Schiff base analogs. The protonated retinal Schiff base analogs show an increased conjugation reflected in the bond orders, bond lengths, and in the decrease in the HOMO-LUMO gap. The nodal characteristics of the HOMO of the protonated retinal Schiff base analog also indicate a strong conjugation in the vicinity of the protonated nitrogen. Based on the results of calculations at the correlated level, the sudden polarization charge transfer mechanism is shown to be an artifact of HF-based methods used in the calculations. Utilisant des mCthodes ab initio en champ auto-cohhent et a des niveaux permettant d'Ctablir une corrtlation, on a CtudiC les propriCtCs a 1'Ctat fondamental (longueurs des liaisons, ordres des liaisons, distributions des charges atomiques nettes) des divers isomkres cis et trans d'analogues du retinal. On a aussi CtudiC l'effet de la protonation sur les propriCtts d'analogues des bases de Schiff du rCtinal. On a observk une convergence des diverses proprittts avec une augmentation de la longueur de la chaine et cette observation justifie l'utilisation d'analogues plus petits qui reproduisent les proprittCs du rCtinal; toutefois, la convergence est plus lente pour les analogues protonCs des bases de Schiff du retinal. Les analogues protones des bases de Schiff du rCtinal prksentent une plus grande conjugaison qui se rkflkte dans les ordres et les longueurs des liaisons et par une diminution de la diffkrence entre la haute occupCe et la basse vacante. Les caracttristiques nodales de la haute occupte de I'analogue proton6 de la base de Schiff du rttinal suggkrent qu'il existe une forte conjugaison au voisinage de I'azote protont. En se basant sur les rCsultats de ces calculs aux niveaux oh l'on peut ttablir une corrklation, on dCmontre que la polarisation soudaine dans le mkcanisme de transfert de charge n'a pas de signification physique et qu'elle est inhCrente aux mkthodes basCes sur HF qui sont utilistes dans les calculs.[Traduit par la revue]

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Section: It Is Evident Fromsupporting

confidence: 90%

Effect of protonation on the ground state properties of retinal analogs: an ab-initio study

Poirier¹,

Yadav²,

Śurján³

1987

Can. J. Chem.

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“…Moreover, the spectra shown in Figure 2 reveal that neither the position nor the intensity of the band at 1608 cm −1 are sensitive to the addition of TFA. Thus in agreement with Smith et al 56 and the computed ν(C=C) frequency of nSBR we assign the band to the stretching of the C=C bonds of retinal.…”

Section: Titration Of Nsbr With Tfasupporting

confidence: 91%

“…In the neutral nSBR molecule, the ν(C=N) vibration is present as a weak band at 1652 cm −1 . 56 This oscillator, being directly involved in hydrogen bonding with TFA and consequent protonation, suffers changes in both c(TFA)/c(nSBR) concentration regimes. As a matter of fact six distinct bands are evident in the 2D correlation maps.…”

Section: Titration Of Nsbr With Tfamentioning

confidence: 99%

Localization of the Counterion of the Protonated Schiff Base of n-butylretinal in Solution

Biliškov¹,

Novak²,

Petković³

et al. 2011

Croat. Chem. Acta

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Abstract. The vibrational spectra of the protonated Schiff base of n-butylretinal (nSBR + ) in dichloromethane are studied. The trifluoroacetic acid (TFA) is used for the protonation of the Schiff base of nbutylretinal (nSBR). Combining the two-dimensional correlation analysis of the experimental infrared spectra with anharmonic frequency calculations it is shown that two types of ionic aggregates between nSBR + and the TFA counterion are formed. The study suggests that the interaction between nSBR + and the TFA counterion may be responsible for the observed lost of photoselectivity in the trans-cis isomerization of the nSBR + in solution. (doi: 10.5562/cca1826)

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“…The band at 1200 cm À1 which has predominantly C 14 -C 15 character, coincides with that of BR. Though the band at 1162 cm À1 (mainly from the C 10 -C 11 stretch [27]) is downshifted by 5 cm À1 with respect to BR, these two bands demonstrate the predominance of all-trans retinal in the heterologously expressed SRII from H. salinarum. The occurrence of the weak band at 1184 cm À1 indicates the presence of low amounts of 13-cis retinal in the dark-adapted protein.…”

Section: Resonance Raman Spectroscopymentioning

confidence: 86%

Functional characterization of sensory rhodopsin II from Halobacterium salinarum expressed in Escherichia coli

et al. 2005

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Sensory rhodopsin II (SRII) from Halobacterium salinarum is heterologously expressed in Escherichia coli with a yield of 3-4 mg of purified SRII per liter cell culture. UV/ Vis absorption spectroscopy display bands characteristic for native SRII. The resonance Raman spectrum provides evidence for a strongly hydrogen-bonded Schiff base like in mammalian rhodopsin but unlike to the homologous pSRII from Natronobacterium pharaonis. Laser flash spectroscopy indicates that SRII in detergent as well as after reconstitution into polar lipids shows its typical photochemical properties with prolonged photocycle kinetics. The first functional heterologous expression of SRII from H. salinarum provides the basis for studies with its cognate transducer HtrII to investigate the molecular processes involved in phototransduction as well as in chemotransduction.

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Vibrational analysis of the all-trans retinal protonated Schiff base

Cited by 120 publications

References 25 publications

Effect of protonation on the ground state properties of retinal analogs: an ab-initio study

Effect of protonation on the ground state properties of retinal analogs: an ab-initio study

Localization of the Counterion of the Protonated Schiff Base of n-butylretinal in Solution

Functional characterization of sensory rhodopsin II from Halobacterium salinarum expressed in Escherichia coli

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