| 1. |
- Drescher, Simon, et al.
(author)
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General Synthesis and Aggregation Behaviour of a Series of Single-Chain 1,ω-Bis(phosphocholines)
- 2007
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In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 13:18, s. 5300-5307
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Journal article (peer-reviewed)abstract
- The synthesis and physicochem. characterization of a series of polymethylene-1,w-bis(phosphocholines) with even-numbered chain lengths between 22 and 32 carbon atoms is described. Two new synthetic strategies for the prepn. of long-chain 1,wo-diols as hydrocarbon building blocks are presented. The temp.-dependent self-assembly of the single-chain bolaamphiphiles was investigated by cryo transmission electron microscopy (cryo-TEM), differential scanning calorimetry (DSC), and Fourier transform IR spectroscopy (FTIR).
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| 2. |
- Meister, Anette, et al.
(author)
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Formation of square lamellae by self-assembly of long-chain bolaphospholipids in water
- 2010
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In: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-683X .- 1744-6848. ; 6:6, s. 1317-1324
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Journal article (peer-reviewed)abstract
- The self-assembly process of the symmetric single-chain polymethylene-1,omega-bis(phosphocholine) (PC-C34-PC) with a chain length of 34 carbon atoms and two polar phosphocholine headgroups when put into water is exclusively driven by hydrophobic interactions of the long alkyl chains. This process leads to the formation of a dense network of helical nanofibers and the formation of a hydrogel (Meister et al. J. Phys. Chem. B, 2008, 112, 4506). In contrast, the single-chain bolalipids tetra-and hexatriacontane-1,omega-diyl-bis[2-(dimethylammonio)ethylphosphate] (Me2PE-Cn-Me2PE, n = 34, 36) and the partly deuterated analogue Me2PE-C11-(CD2)12-C11-Me2PE (dMe(2)PE-C34-Me2PE) form a different type of stable aggregate. In a first step, the self-assembly of these long-chain bolalipids in water at room temperature leads to the formation of a dense network of nanofibers which eventually form a hydrogel. Within one day, the nanofibers transform into square lamellae that grow up to an edge length of about 100 nm. Nanofibers are linked to one or two (opposite) corners of the squares leading to the appearance of a kite-like structure. After one week, all fibers have been transformed into square lamellae which are apparently stacked and form a gel cake. Within several weeks, a more compact cake is formed by syneresis, i.e. the expulsion of water.
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| 3. |
- Meister, Anette, et al.
(author)
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Mixing behaviour of a symmetrical single-chain bolaamphiphile with phospholipids
- 2007
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In: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-683X .- 1744-6848. ; 3:8, s. 1025-1031
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Journal article (peer-reviewed)abstract
- The mixing behavior of the sym. long-chain bolaamphiphile dotriacontane-1,1'-diyl-bis-[2-(trimethylammonio)ethylphosphate] (PC-C32-PC) with conventional phospholipids (DPPC, DMPC, and POPC) was investigated by differential scanning calorimetry and transmission electron microscopy. PC-C32-PC by itself forms nanofibers at room temp., which convert to micellar aggregates at higher temps. The length of the bolaamphiphile corresponds roughly to the thickness of a lipid bilayer. However, a significant insertion of the bolaamphiphile into the phospholipid bilayer vesicles was not obsd. in any of the mixed systems. This is apparently due to packing problems caused by the larger space requirement of the phosphocholine headgroups of PC-C32-PC compared to the small cross-sectional area of the alkyl chain. Obviously, the insertion of these bolaamphiphiles into membrane structures with parallel oriented mols. leads to large void vols. because of this packing problem, so that the bolaamphiphiles prefer to self-assemble into fibers, where the chains can get in closer contact. On the other hand, up to a certain molar ratio, double-chain phospholipids can easily be inserted into the hydrophobic pockets of the bolaamphiphile fibers, where they stabilize the fiber structure.
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| 4. |
- Meister, Annette, et al.
(author)
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Temperature-dependent self-assembly and mixing behavior of symmetrical single-chain bolaamphiphiles
- 2008
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In: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 24:12, s. 6238-46
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Journal article (peer-reviewed)abstract
- The temp.-dependent self-assembly and the mixing behavior of sym. single-chain bolaamphiphiles with different polymethylene chain lengths and different headgroup structures were investigated in water by differential scanning calorimetry (DSC), cryo transmission electron microscopy (cryo-TEM), and small angle neutron scattering (SANS). The even-numbered polymethylene-1,w-bis(phosphocholines) (PC-Cn-PC) are known to form nanofibers composed of stretched mols. with an all-trans alkyl chain conformation (Drescher, S.; Meister, A.; Blume, A.; Karlsson, G.; Almgren, M.; Dobner, B. Chem.-Eur. J.2007, 13, 5300-5307). The odd-numbered analogs were synthesized to study a possible even-odd effect of these bolaamphiphiles during their aggregation in water. In addn. to these bolaamphiphiles with phosphocholine headgroups, a new series of polymethylene-1,w-bis(phosphodimethylethanolamines) (Me2PE-Cn-Me2PE) with smaller headgroup sizes was synthesized. These bolaamphiphiles show an addnl. fiber-fiber transition when the alkyl chain length exceeds 26 carbon atoms. The mixing behavior of both types of bolaamphiphiles indicates that differences in the alkyl chain length up to six carbon atoms are tolerated within the fiber structure. The mixing of two Me2PE-Cn-Me2PE or PC-Cn-PC type bolaamphiphiles with different alkyl chain lengths offers the possibility to adjust the temp., where the crosslinking of the fibers is disrupted and where the fibers break apart. As a consequence, temp. switchable hydrogels are obtained that can be fine-tuned for drug delivery applications. The comparison with dotriacontane-1,32-diyl-bis[2-(methylammonio)-ethylphosphate] (MePE-C32-MePE), a new bolaamphiphile with even smaller phosphomonomethylammonio headgroups, illustrates the importance of the headgroup size for the aggregation behavior. This bolaamphiphile self-assembles exclusively into lamellar structures, and this aggregate type persists in mixts. with the fiber forming Me2PE-C32-Me2PE.
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