To investigate the interdigitation and the resulting fluctuation of lipid chains in the deep part of biomembranes, we aimed to develop a new fluorescent probe based on the well-known trans-parinaric acid (t-PA), but with a tetraene near the end of the C24 chain. The probe, tetracosa-16,18,20,22-tetraenoic acid (TCTEA), synthesized mainly by means of reported strategies, was found to better reflect the behavior of lipids in the deeper interior of bilayers than did t-PA. TCTEA could serve as a useful probe for studying the plasma-membrane dynamics of very-long-chain fatty acids, which have recently elicited significant attention in relation to necroptosis.
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References and Notes
1 Y. Umegawa has relocated to another position at the same university: Office of Management and Planning, Osaka University, 1–3, Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
3a
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3b
Chiricozzi E,
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21TCTEA (1)
A mixture of the ester 5 (37.3 mg, 0.0996 mmol), hexane (16.6 mL), and a sat. solution of I2 in hexane (20.4 μL) was stirred under reflux at 45–50 °C for 15 min. The solvent was removed under reduced pressure, and the residue was purified by column chromatography [silica gel, hexane–EtOAc (50:1)] to give ester 6; Rf = 0.71 (hexane–EtOAc, 20:1).
1H NMR (500 MHz, CDCl3): δ = 6.13 (m, 6 H, 6 C=CH), 5.71 (m, 2 H, 2 C=CH–CH2), 3.66 (s, 3 H, OMe), 1.2–2.4 (m, 28 H, 14 CH2).
A flask was charged with ester 6 (0.0288 g, 0.077 mmol), i-PrOH (2.3 mL), THF (0.357 mL), and 1 M aq KOH (4.61 mL), and the mixture was stirred at 35–40 °C for 1.5 h. The resulting mixture was extracted with EtOAc and the extracts were washed with H2O to give 1 as a yellow film: yield: 0.0235 g (0.0652 mmol, 82%); Rf = 0.05 (hexane–EtOAc, 20:1).
1H NMR (500 MHz, CDCl3): δ = 6.13 (m, 6 H, 6 C=CH), 5.71 (m, 2 H, 2 C=CH–CH2), 2.72 (s, 1 H, OH), 1.2–2.4 (m, 28 H, 14 CH2).
22
Tsuchikawa H,
Monji M,
Umegawa Y,
Yasuda T,
Slotte JP,
Murata M.
Langmuir 2022; 38: 5515
27
Umegawa Y,
Yamamoto T,
Dixit M,
Funahashi K,
Seo S,
Nakagawa Y,
Suzuki T,
Matsuoka S,
Tsuchikawa H,
Hanashima S,
Oishi T,
Matsumori N,
Shinoda W,
Murata M.
Sci. Adv. 2022; 8: eabo2658
