Lipid nanotubes and microtubes: experimental evidence for unsymmetrical monolayer membrane formation from unsymmetrical bolaamphiphiles.
Unsymmetrical bolaamphiphiles, omega- [N-beta-D-glucopyranosylcarbamoyl] alkanoic acids, with even-numbered oligomethylene chains (12, 14, 16, 18, and 20 carbons) self-assembled in water to form lipid nano- and microtubes. The tubular assemblies were separated by centrifugation and examined by transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy to study the molecular packing within the tubular membranes. The nanotubes encapsulated the staining reagent phosphotungstate, which revealed them to be hollow cylinders up to several hundred micrometers long with 30-43-nm outer diameters and 14-29-nm inner diameters. By comparing the membrane stacking periodicity obtained from powder X-ray diffraction analysis of the dehydrated tubes with the molecular packing within single crystals, we found that the nanotubes consist of an unsymmetrical monolayer lipid membrane (MLM) in which the molecules are packed in a parallel fashion. This suggests that the inner surface of the nanotubes is covered with carboxy headgroups and the outer surface with 1-glucosamide headgroups. The inner diameters of the lipid nanotubes could be controlled in the range 17.7-22.2 nm in steps of approximately 1.5 nm/two carbons by varying the oligomethylene spacer length. The microtubes had three types of molecular arrangements. The first type was a symmetrical MLM in which the molecules were packed in an antiparallel fashion. The other two types had unsymmetrical MLM stacking with head-to-head and head-to-tail motifs. Increasing the number of oligomethylene spacers stabilized the unsymmetrical MLM structure in both nano- and microtubes.
Masuda
Mitsutoshi
M
Nanoarchitectonics Research Center (NARC), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan. m-masuda@aist.go.jp
Shimizu
Toshimi
T
D002264:Carboxylic Acids / Q000737:chemistry*; D005960:Glucosides / Q000737:chemistry*; D008055:Lipids / Q000737:chemistry*; D008567:Membranes, Artificial; D046529:Microscopy, Electron, Transmission / Q000379:methods; D008958:Models, Molecular; D015394:Molecular Structure; D043942:Nanotubes / Q000737:chemistry*; D010316:Particle Size; D012680:Sensitivity and Specificity; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013499:Surface Properties; D013501:Surface-Active Agents / Q000737:chemistry*; D014961:X-Ray Diffraction
D002264:Carboxylic Acids; D005960:Glucosides; D008055:Lipids; D008567:Membranes, Artificial; D013501:Surface-Active Agents