Liquid crystalline glycosteroids and acyl steroid glycosides (ASG)

ABSTRACT As part of our studies on glycolipidic liquid crystals, we have investigated some molecules comprising a steroid moiety. These systems can exhibit several types of structures depending on their polarity pattern based on the number of polar and non-polar moieties and their resulting molecular shape. Therefore, to aid describing such systems, we have proposed a specific classification based on this polarity pattern. Many compounds in this family are natural products, which possess important biological properties. Some of the compounds have bolaphilic structures, with both a steroid and a fatty alkyl chain attached to the carbohydrate moiety, such as either the β-galactoside BbGL-1 or the α-glucoside α-CAG that are found in the membranes of the pathogens Borrelia burgdorferi and Helicobacter pylori, respectively. In this account, after a brief introduction on liquid crystalline glycolipids, we focus on carbohydrate–steroid hybrids, summarising our previous work on glycosteroids prepared by the CMGL-synthon strategy, and reporting our preliminary results on the thermotropic behaviour of acyl steroid glycosides (ASG), namely cholesteryl 6-O-acyl-β-gluco- and -galacto-pyranosides. Graphical Abstract

[1]  J. Engberts,et al.  From aldoses to liquid crystals and surfactants , 2018 .

[2]  Y. Queneau,et al.  Carbohydrate chemistry : chemical and biological approaches , 2017 .

[3]  L. Soulère,et al.  Carbohydrate steroid hybrid architectures: the viewpoint of amphiphilicity and self-organisation , 2016 .

[4]  Raju S. Thombal,et al.  Sulfonated graphene oxide as highly efficient catalyst for glycosylation , 2016 .

[5]  Y. Queneau,et al.  Synthesis and use of new C-glycosyl bicyclic lactones , 2015 .

[6]  R. Mezzenga,et al.  Fibrillar networks of glycyrrhizic acid for hybrid nanomaterials with catalytic features. , 2015, Angewandte Chemie.

[7]  J. Kovensky,et al.  Cholesteryl and diosgenyl glycosteroids: synthesis and characterization of new smectic liquid crystals. , 2015, Carbohydrate research.

[8]  T. Gianfagna,et al.  Chemistry and biological activity of steroidal glycosides from the Lilium genus. , 2015, Natural product reports.

[9]  I. Mancini,et al.  Chemical constituents and biological activities of the genus Linaria (Scrophulariaceae) , 2015, Natural product research.

[10]  R. Xu,et al.  Neuroprotection by Saponins , 2015, Phytotherapy research : PTR.

[11]  J. Goodby,et al.  Self-organizing behaviour of glycosteroidal bolaphiles: insights into lipidic microsegregation. , 2015, Organic & biomolecular chemistry.

[12]  R. Berisio,et al.  Chemistry of lipid A: at the heart of innate immunity. , 2015, Chemistry.

[13]  D. Newman,et al.  Covalently linked hopanoid-lipid A improves outer-membrane resistance of a Bradyrhizobium symbiont of legumes , 2014, Nature Communications.

[14]  Ryan A. Davis,et al.  Tandem Glycosyl Iodide Glycosylation and Regioselective Enzymatic Acylation Affords 6-O-Tetradecanoyl-α-d-cholesterylglycosides , 2014, Journal of Organic Chemistry.

[15]  Biao Yu,et al.  Chemical synthesis of saponins. , 2014, Advances in carbohydrate chemistry and biochemistry.

[16]  A. Faizal,et al.  Saponins and their role in biological processes in plants , 2013, Phytochemistry Reviews.

[17]  J. Goodby,et al.  Hydrophobic and hydrophilic balance and its effect on mesophase behaviour in hydroxyalkyl ethers of methyl glucopyranoside. , 2013, Chemistry.

[18]  J. Duan,et al.  Structure, bioactivity, and chemical synthesis of OSW-1 and other steroidal glycosides in the genus Ornithogalum. , 2013, Chemical reviews.

[19]  Victoria L. Challinor,et al.  Open-chain steroidal glycosides, a diverse class of plant saponins. , 2013, Natural product reports.

[20]  L. Wessjohann,et al.  Carbohydrate-steroid conjugation by Ugi reaction: one-pot synthesis of triple sugar/pseudo-peptide/spirostane hybrids. , 2012, Carbohydrate research.

[21]  Ryan A. Davis,et al.  Chemoenzymatic synthesis of cholesteryl-6-O-tetradecanoyl-α-D-glucopyranoside: a product of host cholesterol efflux promoted by Helicobacter pylori. , 2012, Chemical communications.

[22]  T. Grindley,et al.  Facile synthesis of a library of Lyme disease glycolipid antigens. , 2012, Organic letters.

[23]  W. Meyerhof,et al.  Human psychometric and taste receptor responses to steviol glycosides. , 2012, Journal of agricultural and food chemistry.

[24]  R. Csuk,et al.  Triterpene/Steroid Glycoconjugates: Natural Occurrence, Synthesis and Biological Activities , 2012 .

[25]  A. Lampi,et al.  Steryl glycosides and acylated steryl glycosides in plant foods reflect unique sterol patterns , 2012 .

[26]  Biao Yu,et al.  Assembly of naturally occurring glycosides, evolved tactics, and glycosylation methods. , 2012, Accounts of chemical research.

[27]  B. Heasley.  Chemical synthesis of the cardiotonic steroid glycosides and related natural products. , 2012, Chemistry.

[28]  W. Cheng,et al.  Helicobacter pylori cholesteryl glucosides interfere with host membrane phase and affect type IV secretion system function during infection in AGS cells , 2012, Molecular microbiology.

[29]  R. Mezzenga,et al.  Edible supramolecular chiral nanostructures by self-assembly of an amphiphilic phytosterol conjugate , 2012 .

[30]  K. Schrick,et al.  Steryl Glucoside and Acyl Steryl Glucoside Analysis of Arabidopsis Seeds by Electrospray Ionization Tandem Mass Spectrometry , 2012, Lipids.

[31]  Biao Yu,et al.  Assembly of digitoxin by gold(I)-catalyzed glycosidation of glycosyl o-alkynylbenzoates. , 2011, The Journal of organic chemistry.

[32]  S. Suh,et al.  Crystal structure of the catalytic domain of cholesterol‐α‐glucosyltransferase from Helicobacter pylori , 2011, Proteins.

[33]  V. Stonik,et al.  Steroid glycosides from marine organisms , 2011, Steroids.

[34]  Y. Queneau,et al.  Generation of well‐defined clickable glycopolymers from aqueous RAFT polymerization of isomaltulose‐derived acrylamides , 2011 .

[35]  Y. Queneau,et al.  Carbohydrate-based lactones: synthesis and applications. , 2011, Topics in current chemistry.

[36]  G. Durand,et al.  Cholesterol-based α-phenyl-N-tert-butyl nitrone derivatives as antioxidants against light-induced retinal degeneration. , 2010, Bioorganic & medicinal chemistry letters.

[37]  Y. Queneau,et al.  Carboxymethyl glycoside lactone (CMGL) synthons: Scope of the method and preliminary results on step growth polymerization of α-azide-ω-alkyne glycomonomers , 2010 .

[38]  Swantje Thiele,et al.  The functions of steryl glycosides come to those who wait: Recent advances in plants, fungi, bacteria and animals. , 2010, Progress in lipid research.

[39]  R. Schumann,et al.  Chemoenzymatic synthesis of a glycolipid library and elucidation of the antigenic epitope for construction of a vaccine against Lyme disease. , 2010, Chemistry.

[40]  H. Wege,et al.  Neutral push-pull chromophores for nonlinear optical imaging of cell membranes. , 2010, Organic & biomolecular chemistry.

[41]  C. Hilton.  BOARD OF SUPERVISORS OF LOUISIANA STATE UNIVERSITY AND AGRICULTURAL AND MECHANICAL COLLEGE , 2010 .

[42]  N. Ono,et al.  Synthesis of tetraglucosyl- and tetrapolyamine-tetrabenzoporphyrin conjugates for an application in PDT. , 2009, Bioorganic & medicinal chemistry.

[43]  J. Goodby,et al.  The unusual self-organising behaviour of a glycosteroidal bolaphile. , 2009, Chemical communications.

[44]  H. Amenitsch,et al.  Self-organization of synthetic cholesteryl oligoethyleneglycol glycosides in water. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[45]  Y. Queneau,et al.  Glycosidic bicyclic lactones as new carbohydrate scaffolds , 2009 .

[46]  Suvarn S. Kulkarni,et al.  Two-step synthesis of the immunogenic bacterial glycolipid BbGL1. , 2008, Organic letters.

[47]  Y. Queneau,et al.  Synthesis of new mono- and disaccharidic carboxymethylglycoside lactones (CMGLs) and their use toward 1,2-bisfunctionalized carbohydrate synthons , 2008 .

[48]  Y. Queneau,et al.  Recent progress in the synthesis of carbohydrate-based amphiphilic materials: the examples of sucrose and isomaltulose. , 2008, Carbohydrate research.

[49]  Biao Yu,et al.  Total synthesis of lobatoside E, a potent antitumor cyclic triterpene saponin. , 2008, Journal of the American Chemical Society.

[50]  J. Slotte,et al.  Glycosylation induces shifts in the lateral distribution of cholesterol from ordered towards less ordered domains. , 2008, Biochimica et biophysica acta.

[51]  A. Osbourn,et al.  Sad3 and Sad4 Are Required for Saponin Biosynthesis and Root Development in Oat[W] , 2008, The Plant Cell Online.

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

[53]  M. Kalinowska,et al.  Lipase-catalyzed regioselective synthesis of steryl (6′-O-acyl)glucosides , 2007, Biotechnology Letters.

[54]  G. Mackenzie,et al.  Synthesis and Thermotropic Behavior of Simple New Glucolipid Amides , 2007 .

[55]  G. Mackenzie,et al.  Shape dependence in the formation of condensed phases exhibited by disubstituted sucrose esters. , 2007, Chemistry.

[56]  Y. Queneau,et al.  Sucrose chemistry and applications of sucrochemicals. , 2007, Advances in carbohydrate chemistry and biochemistry.

[57]  J. Barrault,et al.  Selective synthesis of amphiphilic hydroxyalkylethers of disaccharides over solid basic catalysts. Influence of the superficial hydrophilic-lipophilic balance of the catalyst. , 2006 .

[58]  W. Welte,et al.  Liquid‐crystalline glycolipids: towards understanding the roles of liquid crystals in biological and life processes , 2006 .

[59]  Y. Queneau,et al.  Concentration measurements of sucrose and sugar surfactants solutions by using the 1H NMR ERETIC method. , 2006, Carbohydrate research.

[60]  R. Templer,et al.  Inverse lyotropic phases of lipids and membrane curvature , 2006, Journal of physics. Condensed matter : an Institute of Physics journal.

[61]  V. Sol,et al.  Synthesis of New Glucosylated Porphyrins Bearing an α‐d‐Linkage , 2006 .

[62]  G. Mackenzie,et al.  Self-organizing properties of monosubstituted sucrose fatty acid esters: the effects of chain length and unsaturation. , 2006, Chemistry.

[63]  Y. Queneau,et al.  Preparation of new amide-linked pseudodisaccharides by the carboxymethylglycoside lactone (CMGL) strategy , 2006 .

[64]  V. Pore,et al.  Steroidal conjugates and their pharmacological applications. , 2006, Current medicinal chemistry.

[65]  Y. Queneau,et al.  PFGSE-NMR study of the self-diffusion of sucrose fatty acid monoesters in water. , 2005, Journal of colloid and interface science.

[66]  Y. Maitani,et al.  Application of sterylglucoside-containing particles for drug delivery. , 2005, Current pharmaceutical biotechnology.

[67]  Y. Queneau,et al.  Sucrose esterification under Mitsunobu conditions: evidence for the formation of 6-O-acyl-3′,6′-anhydrosucrose besides mono and diesters of fatty acids , 2004 .

[68]  G. Courtois,et al.  Catalytic etherification of sucrose with 1,2-epoxydodecane: investigation of homogeneous and heterogeneous catalysts , 2004 .

[69]  Y. Queneau,et al.  The chemistry of unprotected sucrose: the selectivity issue , 2004 .

[70]  S. Choe,et al.  Intestinal Transport of Gentamicin with a Novel, Glycosteroid Drug Transport Agent , 1998, Pharmaceutical Research.

[71]  Y. Queneau,et al.  Transesterification of Sucrose in Organic Medium: Study of Acyl Group Migrations , 2003 .

[72]  G. Mackenzie,et al.  A bilayer to monolayer phase transition in liquid crystal glycolipids. , 2003, Chemical communications.

[73]  Y. Queneau,et al.  Straightforward route for anchoring a glucosyl moiety onto nucleophilic species: reaction of amines and alcohols with carboxymethyl 3,4,6-tri-O-acetyl-alpha-D-glucopyranoside 2-O-lactone. , 2003, The Journal of organic chemistry.

[74]  B. Coxon,et al.  A newly discovered cholesteryl galactoside from Borrelia burgdorferi , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[75]  J. Montero,et al.  A convenient synthetic route to mannose 6‐phosphonate—cholesteryl conjugate , 2003 .

[76]  Y. Queneau,et al.  Interfacial aspects of the catalysis of the synthesis of amphiphilic sucrose ethers from 1,2-epoxydodecane and 1,2-epoxydodecan-3-ol in water , 2002 .

[77]  Y. Queneau,et al.  Winsor behaviour of sucrose fatty acid esters: choice of the cosurfactant and effect of the surfactant composition , 2002 .

[78]  G. Mackenzie,et al.  The effect of molecular shape on the liquid crystal properties of the mono-O-(2-hydroxydodecyl)sucroses , 2001 .

[79]  P. Potier,et al.  Proteinase N-catalysed regioselective esterification of sucrose and other mono- and disaccharides , 2001 .

[80]  Z. Miao,et al.  Synthesis of OSW-1 analogues and a dimer and their antitumor activities. , 2001, Bioorganic & medicinal chemistry letters.

[81]  P. Villa,et al.  The Effect of Molecular Shape and Microphase Segregation on the Formation of Liquid Crystal Phases in Poly-Ols , 2001 .

[82]  J. Montero,et al.  A Mannose-6-phosphonate—Cholesterylamine Conjugate as a Specific Molecular Adhesive Linking Cancer Cells with Vesicles. , 2001 .

[83]  Y. Queneau,et al.  Hydrogen Peroxide Oxidation of Palatinose and Trehalulose: Direct Preparation of Carboxymethyl α‐D‐Glucopyranoside. , 2001 .

[84]  J. Montero,et al.  A mannose-6-phosphonate–cholesterylamineconjugate as a specific molecular adhesive linking cancer cells withvesicles , 2001 .

[85]  P. Potier,et al.  Lipase-Catalysed Selective Synthesis of Sucrose Mixed Diesters , 2001 .

[86]  Y. Queneau,et al.  Study of the competition between homogeneous and interfacial reactions during the synthesis of surfactant sucrose hydroxyalkyl ethers in water , 2000 .

[87]  J. Engberts,et al.  Mesogenic sugars. From aldoses to liquid crystals and surfactants , 2000 .

[88]  T. Nagai,et al.  Electron spin resonance studies of dipalmitoylphosphatidylcholine liposomes containing soybean-derived sterylglucoside. , 2000, Chemical & pharmaceutical bulletin.

[89]  T. Tanaka,et al.  New monoterpene glycoside esters and phenolic constituents of Paeoniae radix, and increase of water solubility of proanthocyanidins in the presence of paeoniflorin. , 2000, Chemical & pharmaceutical bulletin.

[90]  A. Osbourn,et al.  Compromised disease resistance in saponin-deficient plants. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[91]  S. Belniak,et al.  Esterification of unprotected sucrose with acid chlorides in aqueous medium: kinetic reactivity versus acyl- or alkyloxycarbonyl-group migrations , 1999 .

[92]  Y. Queneau,et al.  Synthesis in water of amphiphilic sucrose hydroxyalkyl ethers , 1999 .

[93]  F. Menger,et al.  Digitonin as a Chemical Trigger for the Selective Transformation of Giant Vesicles. , 1998, Angewandte Chemie.

[94]  S. Kelly,et al.  The dependence of mesomorphic behaviour on the extent of hydrogen-bonding in sugar derived polyols , 1998 .

[95]  T. Wagler,et al.  The Efficient Synthesis of a Bis-glycosylated Steroid Drug Transport Reagent: Methyl 3-β-Amino-7α-, 12α-Di(1′α-glucosyl)-5β-cholate (TC002). , 1998 .

[96]  T. Tanaka,et al.  Relationship between hydrophobicity and structure of hydrolyzable tannins, and association of tannins with crude drug constituents in aqueous solution. , 1997, Chemical & pharmaceutical bulletin.

[97]  S. Choe,et al.  Design of compounds that increase the absorption of polar molecules. , 1997, Proceedings of the National Academy of Sciences of the United States of America.

[98]  C. Tschierske.  Molecular self-organization of amphotropic liquid crystals , 1996 .

[99]  T. Irving,et al.  Effects of plant sterols on the hydration and phase behavior of DOPE/DOPC mixtures. , 1995, Biochimica et biophysica acta.

[100]  Takashi Yoshida,et al.  Unique cholesteryl glucosides in Helicobacter pylori: composition and structural analysis , 1995, Journal of bacteriology.

[101]  Yuan Cheng,et al.  Hydrogen Bonding in Micelle Formation , 1994 .

[102]  V. Vill,et al.  A Note on the Melting Point of α-solanine: The solution to a riddle , 1994 .

[103]  R. Miethchen,et al.  Amphiphilic and mesogenic carbohydrates - II. sysnthesis and Characterisation of mono-o-(n-alkyl)-d-glucose derivates , 1992 .

[104]  Y. Mimaki,et al.  SCHUBERTOSIDES A - D, NEW (22S)-HYDROXYCHOLESTANE GLYCOSIDES FROM ALLIUM SCHUBERTII , 1991 .

[105]  T. Fujioka,et al.  Studies on the Constituents of Actinostemma lobatum MAXIM. V. : Structures of Lobatosides B, E, F and G, the Dicrotalic Acid Esters of Bayogenin Bisdesmosides Isolated from the Herb , 1989 .

[106]  A. Eckert,et al.  First carbohydrate liquid crystals of columnar structure , 1989 .

[107]  V. Vill,et al.  Studies on liquid-crystalline glycosides , 1989 .

[108]  R. Kasai,et al.  Solubilizing Properties of Glycyrrhizin and Its Derivatives : Solubilization of Saikosaponin-a, the Saponin of Bupleuri Radix , 1988 .

[109]  N. Yata,et al.  Interaction of saponin of bupleuri radix with ginseng saponin: solubilization of saikosaponin-a with chikusetsusaponin V (= ginsenoside-Ro). , 1985, Chemical & pharmaceutical bulletin.

[110]  J. Goodby.  Liquid Crystal Phases Exhibited by Some Monosaccharides , 1984 .

[111]  Margaret S. Wu,et al.  Synthesis of 6-(5-cholesten-3β-yloxy)hexyl 4-O-(6-deoxy-β-d-galactopyranosyl)-1-thio-β-d-glucopyranoside and derivatives thereof for in vivo liposome studies , 1983 .

[112]  G. A. Jeffrey,et al.  Carbohydrate liquid crystals , 1984 .

[113]  M. Ponpipom,et al.  Glycolipids as potential immunologic adjuvants. , 1980, Journal of medicinal chemistry.

[114]  M. R. Mauk,et al.  Targeting of lipid vesicles: specificity of carbohydrate receptor analogues for leukocytes in mice. , 1980, Proceedings of the National Academy of Sciences of the United States of America.

[115]  M. Ponpipom,et al.  Cell surface carbohydrates for targeting studies , 1980 .

[116]  M. R. Mauk,et al.  Vesicle targeting: timed release and specificity for leukocytes in mice by subcutaneous injection. , 1980, Science.

[117]  J. Mudd,et al.  Effect of steryl glycosides on the phase transition of dipalmitoyl lecithin. , 1980, Plant physiology.

[118]  J. C. Chabala,et al.  The preparation of 3-cholesteryl 6-(thioglycosyl)hexyl ethers and their incorporation into liposomes , 1978 .

[119]  Robert H. White,et al.  Cholesterol β-d-glucoside-6'-O-palmitate, a metabolite of Pythium sylvaticum , 1977 .

[120]  T. Mcmorris,et al.  Cholesterol beta-D-glucoside-6'-O-palmitate, a metabolite of Pythium sylvaticum. , 1977, Biochimica et biophysica acta.

[121]  C. Grunwald,et al.  Acylated Steryl Glycoside Synthesis in Seedlings of Nicotiana tabacum L. , 1976, Plant physiology.

[122]  C. Grunwald.  Effects of free sterols, steryl ester, and steryl glycoside on membrane permeability. , 1971, Plant physiology.

[123]  D. Parke,et al.  The preparation and chemical properties of some glucuronyl esters of β-glycyrrhetic acid (3β-hydroxy-11-oxo-olean-12-en-30-oic acid) and its derivatives , 1970 .

[124]  M. Lepage.  ISOLATION AND CHARACTERIZATION OF AN ESTERIFIED FORM OF STERYL GLUCOSIDE. , 1964, Journal of lipid research.

[125]  A. Salway.  CVIII.—The synthetical preparation of the d-glucosides of sitosterol, cholesterol, and some fatty alcohols , 1913 .