Homogeneous Catalytic Deuteration of Fatty Acyl Chains as a Tool to Detect Lipid Phase Transitions in Specific Membrane Domains: A Fourier Transform Infrared Spectroscopic Study

Török, Zsolt; Szalontai, Balázs; Joó, Ferenc; Wiström, Christina Aurell; Vigh, László Gergely

doi:10.1006/bbrc.1993.1446

Cited by 17 publications

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“…Indeed, C−D labels have been site-selectively incorporated into the proteins cytochrome c − and dihydrofolate reductase and are used to provide high structural and temporal resolution of folding and/or dynamics. Although the use of CD probes in linear IR ,− and 2DIR ,,, spectroscopies is challenging due to their relatively small extinction coefficients, this did not prevent the observation of cross peaks between the CD and CN modes in the small molecule acetonitrile- d 3 , where the extinction coefficient of the symmetric CD 3 stretching mode is ca. 1 M −1 cm −1 , or between the CD and CO modes in formamide- d 3 and in benzaldehyde- d 6 …”

Section: Introductionmentioning

confidence: 99%

C−D Modes of Deuterated Side Chain of Leucine as Structural Reporters via Dual-frequency Two-dimensional Infrared Spectroscopy

et al. 2009

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Perdeuteration of the side chains of amino acids such as leucine results in appearance of reasonably strong absorption peaks around 2050-2220 cm(-1) that belong to the CD stretching modes and exhibit extinction coefficients of up to 120 M(-1) cm(-1). The properties of the CD stretching transitions in leucine-d(10) as structural labels are studied via the methods of two-dimensional infrared (2DIR) spectroscopy. The cross peaks caused by interactions of the CD stretching modes with amide I (Am-I), CO, and amide II (Am-II) modes are obtained by the dual-frequency 2DIR method. The CD stretching peaks in leucine-d(10) are characterized using DFT computational modeling as well as relaxation-assisted 2DIR (RA 2DIR) measurements. The RA 2DIR measurements showed different enhancements and different energy transport times (arrival times) for different CD/Am-II and CD/CO cross peaks; a correlation between the intermode distance, the arrival time, and the amplification factor is reported. We demonstrated that the CD transitions of leucine-d(10) amino acid can serve as convenient structural reporters via the dual-frequency 2DIR methods and discussed the potential of leucine-d(10) and other amino acids with deuterium-labeled side chains as probes of protein structure and dynamics.

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Section: Introductionmentioning

confidence: 99%

C−D Modes of Deuterated Side Chain of Leucine as Structural Reporters via Dual-frequency Two-dimensional Infrared Spectroscopy

et al. 2009

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“…Vibrational spectroscopy can offer small probes and high temporal resolution. C–H stretching modes of methylene groups were found to be useful to probe lipid conformations in lipids, allowing to discriminate between gauche- and anti-conformations. − However, atomic assignment using CH stretching modes is difficult due to vibrational coupling of different methylene groups along the chain. Two-dimensional infrared (2DIR) spectroscopy has emerged as a tool for elucidating molecular interactions and structural dynamics, including those of the lipid bilayers. − Molecular motions of a cell membrane, including the motions on an ultrafast scale, are essential for the cell to conduct its biological function.…”

Section: Introductionmentioning

confidence: 99%

Probing the Hydrophobic Region of a Lipid Bilayer at Specific Depths Using Vibrational Spectroscopy

Islam,

Nawagamuwage,

Parshin

et al. 2023

J. Am. Chem. Soc.

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Separable contributions of ordered and disordered lipid fatty acyl chain segments to νCH ₂ bands in model and biological membranes: A Fourier transform infrared spectroscopic study

1999

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In this article, the assignment of the ν(CH) stretching region of lipid molecules is revisited. This region is extensively used to follow lipid phase transitions, and especially the frequency shifts and bandwidth alterations in the νsymCH2 band have been utilized in this respect. Here, we propose and prove that behind these phenomena there are pairs of component bands in the cases of both the νsymCH2 and the νasCH2 bands. The lower‐frequency components of the pairs are assigned to the vibrations of CH2 groups on trans segments of the fatty acyl chains, while the higher‐frequency components of the pairs are assigned to CH2 groups on gauche segments. To prove these assignments, we have shown that the νCH2 frequencies are characteristic of the conformation of the lipid fatty acyl chain itself, and not the state of the whole lipid matrix. Curve fitting in fact revealed the conformer‐specific components. With the use of singular value decomposition analysis we have demonstrated that the relative intensity changes in the components, and not the shifts in the whole bands, cause the observed shifts in the νCH2 bands upon lipid phase transition. The results of this approach are presented for deuterium‐saturated dioleoyl–phosphatidylcholine mixtures, for the gel → liquid‐crystalline phase transition of dipalmitoyl–phosphatidylcholine multilayers, and for a biological membrane, barley thylakoid. This refined assignment offers physically plausible reasoning for the observed phenomena and is able to explain frequency shifts and bandwidth changes observed previously upon lipid phase transitions, including their nonconcerted temperature dependences. In biological membranes, this interpretation allows the separation of protein‐ and membrane‐dynamics‐induced lipid conformational changes. © 1999 John Wiley & Sons, Inc. Biospectroscopy 5: 169–178, 1999

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Homogeneous Catalytic Deuteration of Fatty Acyl Chains as a Tool to Detect Lipid Phase Transitions in Specific Membrane Domains: A Fourier Transform Infrared Spectroscopic Study

Cited by 17 publications

References 0 publications

C−D Modes of Deuterated Side Chain of Leucine as Structural Reporters via Dual-frequency Two-dimensional Infrared Spectroscopy

C−D Modes of Deuterated Side Chain of Leucine as Structural Reporters via Dual-frequency Two-dimensional Infrared Spectroscopy

Probing the Hydrophobic Region of a Lipid Bilayer at Specific Depths Using Vibrational Spectroscopy

Separable contributions of ordered and disordered lipid fatty acyl chain segments to νCH ₂ bands in model and biological membranes: A Fourier transform infrared spectroscopic study

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Homogeneous Catalytic Deuteration of Fatty Acyl Chains as a Tool to Detect Lipid Phase Transitions in Specific Membrane Domains: A Fourier Transform Infrared Spectroscopic Study

Cited by 17 publications

References 0 publications

C−D Modes of Deuterated Side Chain of Leucine as Structural Reporters via Dual-frequency Two-dimensional Infrared Spectroscopy

C−D Modes of Deuterated Side Chain of Leucine as Structural Reporters via Dual-frequency Two-dimensional Infrared Spectroscopy

Probing the Hydrophobic Region of a Lipid Bilayer at Specific Depths Using Vibrational Spectroscopy

Separable contributions of ordered and disordered lipid fatty acyl chain segments to νCH 2 bands in model and biological membranes: A Fourier transform infrared spectroscopic study

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Separable contributions of ordered and disordered lipid fatty acyl chain segments to νCH ₂ bands in model and biological membranes: A Fourier transform infrared spectroscopic study