Double-chain Ammonium Amphiphiles Research Articles

Perspectives: Synthetic Bilayer Membrane and Giant Nanomembrane.

This is a short story of the beginning of our research on bilayer assembly and its subsequent developments. Inspired by the fluid mosaic model of the cell membrane, we started in the mid 1970's to look for the synthetic counterpart of membrane-forming biolipids. It was soon found by electron microscopy that the stable molecular bilayer was formed from double-chain ammonium amphiphiles. This finding was extended to a number of related types of compounds, thus establishing that the bilayer formation itself was general physicochemical phenomena. The same concept was applicable to non-aqueous systems. The molecular scale thickness-one of the unique features of the biological membrane-was partially reproduced by development of giant nanomembranes. Finally, prospects and some unsolved problems are discussed.

Reversible Photocontrollable Magnetic Vesicles Consisting of Azobenzene

Photochromic magnetic vesicles have been designed by intercalation of Prussian blue into a lipid bilayer membrane which consists of azobenzene. Reversible photoisomerization of the solid system realized reversible photocontrol of the magnetic properties. Here, we have synthesized an amphiphile azo moiety containing a long alkyl chain, and we have prepared photochromic magnetic vesicles consisting of only this azo moiety. As a result, the magnetic property change brought about by visible light illumination was estimated to be ca. 13%, which is much larger than the figure achieved for the similar system that we reported previously (∼1%), which contained the double-chain ammonium amphiphile (J. Am. Chem. Soc. 1999, 121, 3745.).

Bilayer Formation in Ethanol from Dialkylammonium Amphiphile Appended with Nitroaniline Moiety

Abstract A double-chain ammonium amphiphile with the p-nitroaniline moiety formed ordered bilayer assemblies in ethanol media. p-Toluenesulfonate counterion effectively stabilized the bilayer. Excitonic interaction among highly oriented chromophores at the bilayer surface was probed by absorption and circular dichroism spectra.

Monomer Transfer and Solubilization of Bilayer Vesicles from Double-Chained Ammonium Amphiphiles Carrying Aromatic Units

Double-chained ammonium amphiphiles with terminal (4‘-cyanobiphenyl-4-yl)oxy, (4‘-cyanoazobenzen-4-yl)oxy, or (4‘-nitroazobenzen-4-yl)oxy moieties form vesicles upon sonication in water. The UV absorption maxima of the vesicle dispersions are blue shifted due to formation of H aggregates of the aromatic units in the bilayer. When these vesicles are mixed with dialkyldimethylammonium bromide vesicles the H aggregates disappear, as can be monitored by UV spectroscopy. By changing the concentration of both vesicle dispersions, it was concluded that the spectral changes are due to a monomer exchange process instead of a vesicle fusion process. The same phenomenon was used to monitor the solubilization of these vesicles by hexadecyltrimethylammonium bromide micelles. For vesicles from amphiphiles with (cyanobiphenylyl)oxy units at the termini of both chains, a unidirectional diffusion of monomers to didodecyldimethylammonium bromide vesicles is found. The reverse process is hampered by the rigidity of the bilayer of the former compound due to stacking of the aromatic units. For vesicles from amphiphiles with only one azobenzene unit, the exchange with didodecyldimethylammonium bromide vesicles is bidirectional, due to the reduced rigidity of these membranes. The monomer exchange with dodecyloctadecyldimethylammonium bromide and dioctadecyldimethylammonium bromide vesicles is again a unidirectional diffusion of the azobenzene-containing amphiphiles. Solubilization of vesicles from amphiphiles with (cyanobiphenylyl)oxy units at the termini of both chains by hexadecyltrimethylammonium bromide micelles is an unidirectional diffusion process of monomers from the vesicles to the micelles. Solubilization of vesicles from amphiphiles with only one azobenzene unit is accompanied by penetration of hexadecyltrimethylammonium bromide monomers into the bilayers.

Effects of Polymerization on Chromophore Stacking in Bilayer Membranes

Two novel polymerizable double-chained ammonium amphiphiles carrying mesogenic cyanobiphenylyloxy units have been synthesized containing methacrylate in the headgroup or diacetylene groups in the hydrophobic tails. These compounds form bilayer vesicles upon dispersion in water. Polymerization increases the vesicle stability toward solubilization by a nonionic surfactant. The stacking of the cyanobiphenylyloxy units in the bilayer is directly monitored by the extent of the blue shift of the absorption maximum. Upon polymerization a decrease in blue shift is observed, reflecting a decrease in the ordering of the amphiphile molecules. This effect is stronger when polymerization occurs in the hydrophobic tails than in the headgroup region.

Effects of Introduction of Mesogenic Units in Ammonium Amphiphiles on the Aggregation Behavior in Water

A number of novel single- and double-chained ammonium amphiphiles with biphenyl, azobenzene, and stilbene mesogenic moieties at the terminus of one of the hydrophobic tails have been synthesized. The single-chained compounds form less developed bilayers or micellelike structures. The aggregate stability increases from biphenyl- to stilbene- to azobenzene-containing amphiphiles. This increased stability does not correlate with increased hydrophobicity or dipole moment, but correlates with increasing enthalpic contributions. These are attributed to favorable π-π stacking interactions between the mesogenic units. The double-chained compounds form stable bilayer vesicles upon dispersion in water. In the bilayers the mesogens from molecules of opposite leaflets of the bilayer are interdigitated. Bilayers from the azobenzene containing double-chained amphiphiles exhibit a gel-to-liquid crystalline phase transition. Also a blue-shifted UV-absorption maximum is observed, indicating that the mesogens are stacked into H-aggregates. The single-chained amphiphiles readily form aggregates with sodium dodecyl sulfate. These so-called ion-pair amphiphiles form unstable bilayer vesicles.

Chiral Synthesis of a Co(III) Complex on Ammonium Bilayer Templates

Abstract Bilayer membranes of chiral double-chain ammonium amphiphiles incorporated an anionic tridentate ligand in enantiomeric orientations, as confirmed by induced circular dichroism. Complexation of aqueous CoSO4 with the bilayer-bound ligand led to formation of chiral Co(III) complexes.

Direct Observation of Ordered Bilayers in Cast Films of Double-Chain Ammonium Amphiphiles by Transmission Electron Microscopy

Abstract Individual molecular bilayers in cast films of double-chain amphiphiles were observed directly by transmission electron microscopy upon appropriate staining. Ordering of bilayers was affected by a minor structure change of the component amphiphile.

Aggregation behavior of double-chained ammonium amphiphiles containing (cyanobiphenylyl)oxy units

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAggregation behavior of double-chained ammonium amphiphiles containing (cyanobiphenylyl)oxy unitsMarcel D. Everaars, Antonius T. M. Marcelis, and Ernst J. R. SudholterCite this: Langmuir 1993, 9, 8, 1986–1989Publication Date (Print):August 1, 1993Publication History Published online1 May 2002Published inissue 1 August 1993https://doi.org/10.1021/la00032a015RIGHTS & PERMISSIONSArticle Views75Altmetric-Citations19LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

Preparation of a Multilayered Film of Ultrathin Poly(tetraallylammonium bromide) Network

Abstract A multilayered film of two-dimensionally cross linked poly(tetraallylammonium bromide) was prepared using a cast film of bilayers of a double-chain ammonium amphiphile as template. This film displayed unique electrochemical properties.

Multi-Layered Thin Films of Ordered Alumina Particles

Abstract Multi-layered alumina thin films with crystalline anisotropy and high surface area were prepared from ultra-fine particles of alumina using a multi-bilayer cast film of a double-chain ammonium amphiphile as a molecular template.

Correlation between Physicochemical Characteristics of Synthetic Cationic Amphiphiles and Their DNA Transfection Ability

Abstract Liposomes formed with synthetic double-chain ammonium amphiphiles were used for DNA transfection into eukaryotic cells. We studied the correlation between the efficiency of various cationic amphiphiles in DNA transfection and their physicochemical properties. The efficiency of amphiphiles in the transfection was examined by the transient expression of β-galactosidase from its cDNA in COS cells. Amphiphiles with a phase-transition temperature (Tc) lower than 37°C, as measured by differential scanning calorimetry, could introduce DNA into the cells. Electron microscopic observation indicated that amphiphiles possessing DNA transfection ability form vesicular structures in aqueous solution. Thus, fluid and vesicular bilayer structures were much higher than rigid and helical bilayer structures regarding the effectiveness of amphiphiles in DNA transfection. The efficiency of didodecyl N-[p-(2-trimethylammonioethoxy)benzoyl]-l-glutamate bromide was the highest of all the synthetic amphiphiles examined.

Aqueous Bilayers of Glutamate-Based Double-Chain Ammonium Amphiphiles II. Improvement of Polymerization and Membrane Characteristics by Ether-Linked Alkyl Tails

Aqueous Bilayers of Glutamate-Based Double-Chain Ammonium Amphiphiles II. Improvement of Polymerization and Membrane Characteristics by Ether-Linked Alkyl Tails

Template synthesis of two-dimensional network of crosslinked acrylate polymer in a cast multibilayer film

Cast multibilayer films were prepared from aqueous dispersions of a double-chain ammonium amphiphile and a bisacrylate monomer. X-ray diffraction and the structure simulation by electron density matching showed that the lamellar molecular packing in a single-component cas film was modified upon addition of the monomer so that the monomer can be incorporated uniformly into the void near the bilayer surface. The depth profile of element distribution as determined by X-ray photoelectron spectroscopy was consistent with this supposition

Molecular Design of Black Lipid Membranes (BLM) by Polymerized Double-Chain Ammonium Amphiphiles

Abstract Planar bilayer membranes were obtained from polymerized double-chain ammonium amphiphiles. Their properties were closely related to those of the corresponding aqueous bilayers, and a life time longer than one day was observed for a well-organized polymer sample.

Design of spatial disposition of anionic porphyrins in matrices of ammonium bilayer membranes

A methodology to place charged porphyrin derivatives in specific spatial arrangements in matrices of ammonium bilayer membranes was explored. Aqueous mixtures of anionic copper(II) porphyrins and bilayer dispersions of single-chain and double-chain ammonium amphiphiles were cast on Teflon sheets to produce regular multilayer films. The orientation of doped copper(II) porphysins was determined by anisotropies of ESR spectral patterns that were dependent on the disposition of the cast film in the magnetic field

A multilayered film of an ultrathin siloxane network

A multilayered film of an ultrathin siloxane network was prepared from McSi(OMe)3 by using a multi-bilayer cast film of a double-chain ammonium amphiphile as a molecular template.

Polymerization and membrane characteristics of aqueous bilayers of glutamate-based double-chain ammonium amphiphiles

Preparation de composes amphiphiles monoacrylique et diacrylique et etude de leurs caracteristiques de couche bimoleculaire avant et apres photopolymerisation. Obtention de polymeres de masse moleculaire de plusieurs millions, avec un nombre d'agregation peu different de celui du monomere mais une morphologie moins ordonnee. Etude par DSC et spectroscopie de l'organisation moleculaire des couches bimoleculaires polymerisees

Orientation and Distribution of the Carbazole Unit in Monolayers and Their Fluorescence Characteristics

Abstract Double-chain ammonium amphiphiles that contain the carbazole ring formed stable monolayers on water. Their fluorescence patterns indicated different packing modes of the chromophore which depended on chemical structure and component distribution.

Detection of phase transition of thin Langmuir–Blodgett film based on an electrical capacitance measurement

Langmuir–Blodgett films (10 layers) of a double-chain ammonium amphiphile complexed with poly(styrenesulphonate) on a pair of platinum electrodes have been found to show phase transition in aqueous electrolyte solution, which was successfully detected electrochemically by measuring electrical capacitance under applied alternating current.