Initial step of pH-jump-induced lamellar to bicontinuous cubic phase transition in dioleoylphosphatidylserine/monoolein

Electrostatic interactions (EI) are an important factor for phase transitions between lamellar liquid-crystalline (L(α)) and inverse bicontinuous cubic (Q(II)) phases. We investigated the low pH-induced L(α) to double-diamond cubic (Q(II)(D)) phase transition in dioleoylphosphatidylserine (DOPS)/mon...

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Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1992. - 30(2014), 27 vom: 15. Juli, Seite 8131-40
1. Verfasser: Oka, Toshihiko (VerfasserIn)
Weitere Verfasser: Tsuboi, Taka-aki, Saiki, Takahiro, Takahashi, Tomoki, Alam, Jahangir Md, Yamazaki, Masahito
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2014
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article Research Support, Non-U.S. Gov't Glycerides Phosphatidylserines Unilamellar Liposomes 1,2-dioleoylphosphatidylserine 70614-14-1 monoolein C4YAD5F5G6
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245 1 0 |a Initial step of pH-jump-induced lamellar to bicontinuous cubic phase transition in dioleoylphosphatidylserine/monoolein 
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520 |a Electrostatic interactions (EI) are an important factor for phase transitions between lamellar liquid-crystalline (L(α)) and inverse bicontinuous cubic (Q(II)) phases. We investigated the low pH-induced L(α) to double-diamond cubic (Q(II)(D)) phase transition in dioleoylphosphatidylserine (DOPS)/monoolein (MO) using time-resolved small-angle X-ray scattering. Using a stopped-flow apparatus, a suspension of liposomes (multilamellar vesicles (MLVs) or large unilamellar vesicles (LUVs)) of 20%-DOPS/80%-MO membrane at neutral pH was rapidly mixed with a low pH buffer, and then the structural change of the membranes in the resultant suspension was observed as a function of time (i.e., pH-jump experiment). At the initial step, the L(α) phase was directly transformed into the hexagonal II (H(II)) phase, and subsequently, the H(II) phase slowly converted into the Q(II)(D) phase. We obtained the rate constants of the initial step (i.e., the L(α) to H(II) phase transition) and of the second step (i.e., the H(II) to Q(II)(D) phase transition) using the non-negative matrix factorization method. The rate constant of the initial step was independent of the MLV concentration, indicating that single MLVs can convert into the HII phase without any interaction with other MLVs. On the other hand, the rate constant of the initial step increased with a decrease in pH, 0.041 s(-1) at pH 2.6 and 0.013 s(-1) at pH 2.8, and also exhibited a size dependence; for smaller vesicles such as LUVs and smaller MLVs with diameters of ~1 μm, the rate constant was smaller. They were reasonably explained by the classical nucleation theory. These results provide the first experimental evidence of the total kinetics of EI-induced L(α)/Q(II) phase transitions 
650 4 |a Journal Article 
650 4 |a Research Support, Non-U.S. Gov't 
650 7 |a Glycerides  |2 NLM 
650 7 |a Phosphatidylserines  |2 NLM 
650 7 |a Unilamellar Liposomes  |2 NLM 
650 7 |a 1,2-dioleoylphosphatidylserine  |2 NLM 
650 7 |a 70614-14-1  |2 NLM 
650 7 |a monoolein  |2 NLM 
650 7 |a C4YAD5F5G6  |2 NLM 
700 1 |a Tsuboi, Taka-aki  |e verfasserin  |4 aut 
700 1 |a Saiki, Takahiro  |e verfasserin  |4 aut 
700 1 |a Takahashi, Tomoki  |e verfasserin  |4 aut 
700 1 |a Alam, Jahangir Md  |e verfasserin  |4 aut 
700 1 |a Yamazaki, Masahito  |e verfasserin  |4 aut 
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773 1 8 |g volume:30  |g year:2014  |g number:27  |g day:15  |g month:07  |g pages:8131-40 
856 4 0 |u http://dx.doi.org/10.1021/la5021719  |3 Volltext 
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