Amphitropic liquid crystal phases from polyhydroxy sugar surfactants: Fundamental studies

The self-assembly phenomena on a special class of poly-hydroxy sugar surfactant have been studied extensively. This class of material is classified as amphitropic liquid crystals since they exhibit both thermotropic and lyotropic liquid crystalline properties. Hence the potential applications of these non-ionic surfactants are more versatile than those from the conventional lyotropic liquid crystals including those from thermotropic phases, but the latters are yet to be realized. Unfortunately, due to the lack of interest (or even awareness), fundamental studies in thermotropic glycolipids are scanty to support application development, and any tangible progress is often mired by the complexity of the sugar stereochemistry. However, some applications may be pursued from these materials by taking the advantage of the sugar chirality and the tilted structure of the lipid organization which implies ferroelectric behavior. Here, we present our studies on the stereochemical diversity of the sugar units in glycosides that form the thermotropic/lyotropic phases. The structure to property relationship compares different chain designs and other popular polyhydroxy compounds, such as monooleins and alkylpolyglucosides. Different structural properties of these glycosides are discussed with respect to their self-assembly organization and potential applications, such as delivery systems and membrane mimetic study.

[1]  S. Gruner,et al.  Differential scanning calorimetry and X-ray diffraction studies of the thermotropic phase behavior of the diastereomeric di-tetradecyl-beta-D-galactosyl glycerols and their mixture. , 1994, Biophysical journal.

[2]  A. O'lenick.  Guerbet chemistry , 2001 .

[3]  Patrick Stoller,et al.  Polarization-modulated second harmonic generation in collagen. , 2002, Biophysical journal.

[4]  H. Takezoe,et al.  Columnar liquid crystal with a spontaneous polarization along the columnar axis. , 2010, Journal of the American Chemical Society.

[5]  S. Gruner,et al.  The physical properties of glycosyl diacylglycerols. Calorimetric, X-ray diffraction and Fourier transform spectroscopic studies of a homologous series of 1,2-di-O-acyl-3-O-(beta-D-galactopyranosyl)-sn-glycerols. , 2001, Chemistry and physics of lipids.

[6]  B. Halle,et al.  Interpretation of magnetic resonance data from water nuclei in heterogeneous systems , 1981 .

[7]  S. Gruner,et al.  The thermotropic phase behaviour and phase structure of a homologous series of racemic beta-D-galactosyl dialkylglycerols studied by differential scanning calorimetry and X-ray diffraction. , 2007, Chemistry and physics of lipids.

[8]  S. Gruner,et al.  Effect of the chirality of the glycerol backbone on the bilayer and nonbilayer phase transitions in the diastereomers of di-dodecyl-beta-D-glucopyranosyl glycerol. , 1992, Biophysical journal.

[9]  R. Bryce,et al.  Molecular dynamics study of anhydrous lamellar structures of synthetic glycolipids: effects of chain branching and disaccharide headgroup. , 2012, The journal of physical chemistry. B.

[10]  B. Ninham,et al.  Theory of self-assembly of hydrocarbon amphiphiles into micelles and bilayers , 1976 .

[11]  L. Cantu',et al.  Self-assembly in glycolipids , 2007 .

[12]  T. Kitayama,et al.  7: Definitions of Basic Terms Relating to Low-Molar-Mass and Polymer Liquid Crystals (2001) , 2009 .

[13]  B. A. Timimi,et al.  Deuterium NMR Investigation of the lyotropic phases of alkyl β-glycoside/D2O systems. , 2013, The journal of physical chemistry. B.

[14]  C. Vicent,et al.  Molecular Recognition of Carbohydrates Using a Synthetic Receptor. A Model System to Understand the Stereoselectivity of a Carbohydrate-Carbohydrate Interaction in Water , 1995 .

[15]  Quantitative analysis of the packing of alkyl glycosides: a comparison of linear and branched alkyl chains , 2010 .

[16]  H. Høiland,et al.  STEREOCHEMICAL ASPECTS OF HYDRATION OF CARBOHYDRATES IN AQUEOUS-SOLUTIONS .3. DENSITY AND ULTRASOUND MEASUREMENTS , 1991 .

[17]  K. Tamada,et al.  Self-assembly of synthetic glycolipid/water systems. , 1999, Advances in colloid and interface science.

[18]  D. Scherman,et al.  New Synthetic Glycolipids for Targeted Gene Transfer: Synthesis, Formulation in Lipoplexes and Specific Interaction with Lectin , 2004, Drug delivery.

[19]  C. Conn,et al.  Investigation of the effect of sugar stereochemistry on biologically relevant lyotropic phases from branched-chain synthetic glycolipids by small-angle X-ray scattering. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[20]  V. Vill,et al.  The stereochemistry of glycolipids. A key for understanding membrane functions? , 2006 .

[21]  G. Lindblom,et al.  Lipid and water diffusion in bicontinuous cubic phases measured by NMR. , 1993, Biophysical journal.

[22]  G. Tiddy,et al.  Interaction of water and oxyethylene groups in lyotropic liquid-crystalline phases of poly(oxyethylene) n-dodecyl ether surfactants studied by 2H nuclear magnetic resonance spectroscopy , 1984 .

[23]  A. Belcher,et al.  Chiral smectic C structures of virus-based films , 2003 .

[24]  R. Templer,et al.  Calculations of and evidence for chain packing stress in inverse lyotropic bicontinuous cubic phases. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[25]  R. Lewis,et al.  Synthesis and thermotropic characterization of a homologous series of racemic beta-D-glucosyl dialkylglycerols. , 2000, Biochimica et biophysica acta.

[26]  B. A. Timimi,et al.  An upper critical point in a lamellar liquid crystalline phase , 1993 .

[27]  O. K. Abou-Zied,et al.  Evidence of Basic Medium in the Polar Nanochannels of the Inverse Bicontinuous Cubic Phase of a Guerbet Glycolipid: A Steady-State and Time-Resolved Fluorescence Study , 2013 .

[28]  G. Mackenzie,et al.  Thermotropic liquid crystalline glycolipids. , 2007, Chemical Society reviews.

[29]  K. Iwasa,et al.  Further studies of rapid mechanical changes in squid giant axon associated with action potential production. , 1982, The Japanese journal of physiology.

[30]  Karlheinz Hill,et al.  Alkyl Polyglycosides-Properties and Applications of a new Class of Surfactants. , 1998, Angewandte Chemie.

[31]  Rusnah Syahila Duali Hussen,et al.  Thermotropic and lyotropic liquid crystalline phases of Guerbet branched-chain -D-glucosides , 2011 .

[32]  C. Sundari,et al.  Polysaccharides as amphiphiles , 1993 .

[33]  A. Ianaro,et al.  Glycolipids from sponges. VII. Simplexides, novel immunosuppressive glycolipids from the Caribbean sponge Plakortis simplex. , 1999, Bioorganic & medicinal chemistry letters.

[34]  J. Seddon,et al.  Structure of the inverted hexagonal (HII) phase, and non-lamellar phase transitions of lipids. , 1990, Biochimica et biophysica acta.

[35]  R. Hashim,et al.  Nature-like synthetic alkyl branched-chain glycolipids: a review on chemical structure and self-assembly properties , 2012 .

[36]  A. Jákli,et al.  Thermotropic liquid crystalline properties of amphiphilic branched chain glycolipids , 2006 .

[37]  S. Mirzadeh,et al.  A reevaluation of the epimeric and anomeric relationship of glucosides and galactosides in thermotropic liquid crystal self-assemblies. , 2011, Carbohydrate research.

[38]  Caroline A Ericsson,et al.  Solid-state phase behaviour of dodecylglycosides. , 2005, Carbohydrate research.

[39]  R. Lemieux.  Rhône-Poulenc Lecture. The origin of the specificity in the recognition of oligosaccharides by proteins , 1989 .

[40]  V. Vill,et al.  Carbohydrate liquid crystals: structure–property relationship of thermotropic and lyotropic glycolipids , 2002 .

[41]  G. Tiddy,et al.  Phase behaviour of monoglyceride/water systems , 1993 .

[42]  O. K. Abou-Zied,et al.  Characterization of the Head Group and the Hydrophobic Regions of a Glycolipid Lyotropic Hexagonal Phase Using Fluorescent Probes , 2011 .

[43]  O. K. Abou-Zied,et al.  Fluorescence probing of the temperature-induced phase transition in a glycolipid self-assembly: hexagonal ↔ micellar and cubic ↔ lamellar. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[44]  J. P. Holt,et al.  Laser temperature-jump technique for relaxation studies of the ionic conductances in myelinated nerve fibers. , 1972, Biophysical Journal.

[45]  K. Holmberg.  Natural surfactants , 2001 .

[46]  C. C. Huang,et al.  Structures of chiral smectic-C mesophases revealed by polarization-analyzed resonant x-ray scattering. , 1999, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[47]  F. Nilsson,et al.  Physical−Chemical Properties of Some Branched Alkyl Glucosides , 1997 .

[48]  J. Seddon,et al.  Thermotropic and lyotropic phase behaviour of monoalkyl glycosides , 1997 .

[49]  S. Ahmadi,et al.  Atomistic simulation studies of the α/β-glucoside and galactoside in anhydrous bilayers: effect of the anomeric and epimeric configurations , 2014, Journal of Molecular Modeling.

[50]  George A. Jeffrey.  Carbohydrate Liquid Crystals , 1986 .

[51]  Riccardo Baron,et al.  Conformational properties of glucose-based disaccharides investigated using molecular dynamics simulations with local elevation umbrella sampling. , 2010, Carbohydrate research.

[52]  M. Baron.  Definitions of basic terms relating to low-molar-mass and polymer liquid crystals (IUPAC Recommendations 2001) , 2001 .

[53]  Nasrul Zamani Mohd Rodzi,et al.  Branched chain glycosides: Enhanced diversity for phase behavior of easily accessible synthetic glycolipids , 2006 .

[54]  Reinhard Lipowsky,et al.  The conformation of membranes , 1991, Nature.

[55]  S. Singer,et al.  The fluid mosaic model of the structure of cell membranes. , 1972, Science.