INTERACTION OF DIBUCAINEHCl LOCAL ANESTHETICS WITH BACTERIORHODOPSIN IN PURPLE MEMBRANE: A SPECTROSCOPIC STUDY

Lin, C. T.; Chyan, Y. G.; Kresheck, Gordon C.; Bitting, Herbert C.; El‐Sayed, Mostafa A.

doi:10.1111/j.1751-1097.1989.tb08436.x

Cited by 8 publications

(2 citation statements)

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“…When purple membrane is suspended in 60% dimethyl sulfoxide, however, a red species absorbing maximally at 480 nm is formed at or above neutral pH (Pande et al, 1989b;Oesterhelt et al, 1973). The treatment of purple membrane with anesthetics also produces a 480-nm-absorbing species at neutral pH (Nishimura et al, 1985;Lin et al, 1989). This red form (bR480) was previously believed to have a deprotonated Schiff base and confused with the 460-nm-absorbing species appearing at an extremely high pH.…”

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confidence: 99%

Effect of a light-induced pH gradient on purple-to-blue and purple-to-red transitions of bacteriorhodopsin

Nasuda-Kouyama¹,

Fukuda²,

Iio³

et al. 1990

Biochemistry

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Bacteriorhodopsin-containing vesicles that were able to alkalize the extravesicular medium by greater than 1.5 pH units under illumination, i.e., inside-out vesicles, were reconstituted by reverse-phase evaporation with Halobacterium halobium polar lipids or exogenous phospholipids. Acid titration of a dark-adapted sample was accompanied by a color change from purple to blue (pKa = 2.5-4.5 in 0.15 M K2SO4), and alkali titration resulted in the formation of a red species absorbing maximally at 480 nm (pKa = 7 to greater than 9), the pKa values and the extents of these color changes being dependent on the nature of lipid. When a vesicle suspension at neutral or weakly acidic pH was irradiated by continuous light so that a large pH gradient was generated across the membrane, either a purple-to-blue or a purple-to-red transition took place. The light-induced purple-to-red transition was significant in an unbuffered vesicle suspension and correlated with the pH change in the extravesicular medium. The result suggests that the purple-to-red transition is driven from the extravesicular side, i.e., from the C-terminal membrane surface. In the presence of buffer molecules outside, the dominant color change induced in the light was the purple-to-blue transition, which seemed to be due to a large decrease in the intravesicular pH. But an apparently inconsistent result was obtained when the extravesicular medium was acidified by a HCl pulse, which was accompanied by a rapid color change to blue. We arrived at the following explanation: The two bR isomers, one containing all-trans-retinal and the other 13-cis-retinal, respond differently to pH changes in the extravesicular and the intravesicular medium. In this relation, full light adaptation was not achieved when the light-induced purple-to-blue transition was significant; i.e., only the 13-cis isomer is likely to respond to a pH change at the N-terminal membrane surface.

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confidence: 99%

Effect of a light-induced pH gradient on purple-to-blue and purple-to-red transitions of bacteriorhodopsin

Nasuda-Kouyama¹,

Fukuda²,

Iio³

et al. 1990

Biochemistry

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“…that the tertiary amine local anesthetics display rather rich optical properties and, more importantly, the photophysical properties of uncharged and charged species are quite different and clearly distinguishable from one another. Furthermore, we have illustrated (Lin et al, 1987(Lin et al, ,1989 that local anesthetic species exist predominantly as the protonated form, DH+, in hydrophilic environments, and that the equilibrium is shifted to favor the neutral form in hydrophobic environments. This indicates that tertiary amine local anesthetics are viable "direct" emission probes for studying the nature of their solubilization microenvironment in biomembranes.…”

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confidence: 91%

Solubilization Sites and Acid‐base Forms of Dibucaine‐hydrochloride in Neutral and Charged Micellar Solutions

Mertz¹,

Lin²

1991

Photochem & Photobiology

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Steady-state and time-resolved emission spectroscopic techniques have been employed to characterize the drug species of dibucaine and to identify its location in micellar Triton X-100 (neutral), hexadecyltrimethyl ammonium bromide (cationic) and lithium dodecyl sulfate (anionic) solutions at 77 K. Under physiological conditions, the dibucaine is shown to exist in the free base form (D) while solubilized in the hydrocarbon core of neutral micelles. In cationic micellar solution, dibucaine exists as the monocation species (DH+) where the anesthetic is solubilized in the extramicellar aqueous solution and D is solubilized in the hydrophobic region with close proximity to the micellar interface. In the anionic micelles, interfacial solubilization is most consistent with a site in which the tertiary amino group of the monocation dibucaine (DH+) is anchored at the micellar interface with its quinoline analog penetrating the hydrophobic region. The distinct properties observed for the drug species (i.e. D and DH+) and their solubilization sites in micelles are consistent with a balance between hydrophobic forces, surface polarity and the interfacial electrostatic potential present in the micellar solubilization sites. These observations could lend insight into the molecular basis of pharmacological action, in particular the mechanism of local anesthetic drug transport across membranes.

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Theoretical studies on local anesthetics: Procaine, lidocaine, tetracaine, bupivacaine, and dibucaine?neutral and monoprotonated

Neto

Alencastro

1997

Int. J. Quant. Chem.

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Ž .The molecular basis of the pharmacological action of tertiary amine local anesthetics LA is still unclear. However, there is experimental evidence that the LA penetrates into the axon as a neutral form and acts in the charged form from the intracellular phase. In this work we report quantum chemical semiempirical results for the neutral and monoprotonated forms of procaine, lidocaine, tetracaine, bupivacaine, and dibucaine. All geometries have been fully optimized with the AM1 Hamiltonian. Solvent effects were Ž . included at the self-consistent reaction field SCRF approximation. We have found that the most stable conformers of positively charged LA agents are all characterized by intramolecular H-bond formation involving the protonated amine groups. INDOrS-CIS calculations have revealed that the gas-phase absorption spectra of LAs result from the superposition of the spectra of the ring system and the carbonyl, in a large extent Ž . perturbed by intramolecular charge transfer CT . For all studied LAs, the benzene B 2 u bands are very weak and the benzene B bands gain intensity due to symmetry 1u breaking. Formation of intramolecular H bond strongly affects the carbonyl CT bands. On the other hand, the spectrum of dibucaine is dominated by the quinoline system.

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INTERACTION OF DIBUCAINEHCl LOCAL ANESTHETICS WITH BACTERIORHODOPSIN IN PURPLE MEMBRANE: A SPECTROSCOPIC STUDY

Cited by 8 publications

References 50 publications

Effect of a light-induced pH gradient on purple-to-blue and purple-to-red transitions of bacteriorhodopsin

Effect of a light-induced pH gradient on purple-to-blue and purple-to-red transitions of bacteriorhodopsin

Solubilization Sites and Acid‐base Forms of Dibucaine‐hydrochloride in Neutral and Charged Micellar Solutions

Theoretical studies on local anesthetics: Procaine, lidocaine, tetracaine, bupivacaine, and dibucaine?neutral and monoprotonated

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