Lariat Ethers in Membranes and as Membranes

Lariat ethers are macrocyclic (crown ethers) that have one or more sidearms appended to the ring. The sidearms usually contain Lewis basic donor groups when cation binding properties are desired. By combining both a macroring and a sidearm, the advantages of both three-dimensional encapsulation and flexibility are realized. Flexibility is important because cation transport requires rapid complexation and release, especially the latter if it is to be effective. The structural, cation binding, and transport properties are discussed herein. It is also possible to prepare macrocycles having lipophilic sidearms that do not contain any donor group. If lipophilic is enough, these lariat ethers self-assemble into micelles, niosomes, or vesicles. If appropriately designed, these compounds may assemble into smaller, more readily characterized structures. Examples of all of these cases are illustrated herein.

[1]  G. Gokel,et al.  Cation-binding properties and molecular structure of the crystalline complex (aza-12-crown-4)2.cntdot.NaI , 1987 .

[2]  G. Gokel,et al.  A molecular box, based on bibracchial lariat ethers having adenine and thymine sidearms, that self-assembles in water , 1987 .

[3]  A. Ricard,et al.  Influence of the polymer on an anionic activation reaction promoted by a supported crown ether , 1984 .

[4]  H. Mcconnell,et al.  Spin-labeled biomolecules. , 1965, Proceedings of the National Academy of Sciences of the United States of America.

[5]  D. A. Gustowski,et al.  Electrochemical switching of lariat ethers: enhanced cation binding by one- and two-electron reduction of an anthraquinone sidearm , 1986 .

[6]  N. Tietz Fundamentals of Clinical Chemistry , 1970 .

[7]  Sunney I. Chan,et al.  Nuclear magnetic resonance study of the solution structures of some crown ethers and their cation complexes , 1976 .

[8]  I. M. Kolthoff,et al.  Transfer activity coefficients in various solvents of several univalent cations complexed with dibenzo-18-crown-6 , 1980 .

[9]  H. Mcconnell,et al.  Physics and chemistry of spin labels , 1970, Quarterly Reviews of Biophysics.

[10]  D. A. Gustowski,et al.  Geometrical and electronic cooperativity in cation-mediated electrochemical reductions of anthraquinone-substituted podands , 1986 .

[11]  P. Kuo,et al.  Effect of metal salts on the cloud point of alkyl crown compounds , 1980 .

[12]  R. G. Kostyanovsky,et al.  Macroheterocycles. XIV: A convenient synthesis of azacrown ether derivatives via aminomethylation , 1983 .

[13]  A. Florence,et al.  The effect of non‐ionic surfactant vesicle (niosome) entrapment on the absorption and distribution of methotrexate in mice , 1985, The Journal of pharmacy and pharmacology.

[14]  Charles J. Pedersen,et al.  Cyclic polyethers and their complexes with metal salts , 1967 .

[15]  S. Chan,et al.  Cholesterol-phospholipid interaction in membranes. 1. Cholestane spin-label studies of phase behavior of cholesterol-phospholipid liposomes. , 1982, Biochemistry.

[16]  M. S. Kim,et al.  Influence of solvent, anion and presence of nitrogen in the ring structure on the mechanism of complexation of alkali metal cations with crown ethers. , 1987, Biophysical chemistry.

[17]  H. Mcconnell,et al.  Bent fatty acid chains in lecithin bilayers. , 1971, Proceedings of the National Academy of Sciences of the United States of America.

[18]  Evidence from e.s.r. studies for virtual immobility in niosomes derived from steroidal lariat ethers , 1989 .

[19]  G. Gokel,et al.  Ring-sidearm cooperativity in cation inclusion complexes of 12-membered ring lariat ethers: effect of sidearm chain length and a clarification of long-sidearm binding strengths , 1988 .

[20]  J. Simon,et al.  Fast cation transfer at a micelle subsurface: Synthesis and properties of an amphiphilic macrocycle , 1977 .

[21]  D. Eatough,et al.  The Synthesis and Ion Bindings of Synthetic Multidentate Macrocyclic Compounds. , 1974, Chemical reviews.

[22]  D. A. Gustowski,et al.  Contrasting one- and two-cation binding behavior in syn- and anti-anthraquinone bibracchial podand (BiP) mono- and dianions assessed by cyclic voltammetry and electron paramagnetic resonance spectroscopy , 1988 .

[23]  G. Gokel,et al.  Studies directed toward the fabrication of a synthetic cation-conducting channel based on lariat ethers: The feeble forces concept for self-assembly , 1989 .

[24]  D. A. Gustowski,et al.  Electrochemical switching of lariat ethers. Survey of cation binding by neutral and reduced forms of one- and two-armed carbon- and nitrogen-pivot lariat ethers , 1985 .

[25]  H. Tsukube Characteristic Transport Properties of Diaza-crown Ethers for Primary and Secondary Ammonium Cations , 1984 .

[26]  V. T. Ivanov,et al.  Membrane-active complexones , 1974 .

[27]  V. J. Gatto,et al.  Syntheses of calcium-selective, substituted diaza-crown ethers: a novel, one-step formation of bibracchial lariat ethers (BiBLES) , 1984 .

[28]  G. Gokel,et al.  Steroidal lariat ethers: a new class of macrocycles and the crystal structure of N-(cholesteryloxycarbonyl)aza-15-crown-5 , 1987 .

[29]  G. Gokel,et al.  Determination of thermodynamic parameters in lariat ether complexes using ion-selective electrodes , 1987 .

[30]  S. Shinkai,et al.  Proton-driven Ion Transport and Metal-assisted Amino Acid Transport with an Anion-capped Azacrown Ether , 1983 .

[31]  G. Gokel,et al.  Lariat ethers. Synthesis and cation binding of macrocyclic polyethers possessing axially disposed secondary donor groups , 1980 .

[32]  B. Cox,et al.  Kinetics of alkali metal complex formation with cryptands in methanol , 1978 .

[33]  K. Ueno,et al.  CROWN COMPLEXANE. 1,10-DIAZA-4,7,13,16-TETRAOXACYCLOOCTADECANE-N,N′-DIPROPIONIC ACID , 1978 .

[34]  F. Montanari,et al.  Lipophilic [2.2.2]Cryptands as Phase-Transfer Catalysts. Activation and Nucleophilicity of Anions in Aqueous-Organic Two- Phase Systems and in Organic Solvents of Low Polarity , 1979 .

[35]  Wilfred D. Stein,et al.  Transport and Diffusion Across Cell Membranes , 1986 .

[36]  H. Tsukube Specific cation-transport abilities of new macrocyclic polyamine compounds , 1983 .

[37]  W. Hubbell,et al.  Orientation and motion of amphiphilic spin labels in membranes. , 1969, Proceedings of the National Academy of Sciences of the United States of America.

[38]  Å. Åkeson,et al.  Diaza-crown Ethers. I. Alkali Ion Promoted Formation of Diaza-crown Ethers and Syntheses of Some N,N'-Disubstituted Derivatives. , 1979 .

[39]  M. Sisido,et al.  Synthesis, structure, and excimer formation of aromatic cholesteric liquid crystals , 1984 .

[40]  G. Gokel,et al.  Crown cation complex effects. 20. Syntheses and cation binding properties of carbon-pivot lariat ethers , 1983 .

[41]  J. Lehn,et al.  Cryptates. XVI. [2]-Cryptates. Stability and selectivity of alkali and alkaline-earth macrobicyclic complexes , 1975 .

[42]  J. Bradshaw 2 – SYNTHESIS OF MULTIDENTATE COMPOUNDS , 1978 .

[43]  G. Gokel,et al.  Mechanism of complexation of sodium(1+) with N-pivot-lariat 15-crown-5 ethers in methanol at 25.degree.C , 1987 .

[44]  J. Freed 3 – Theory of Slow Tumbling ESR Spectra for Nitroxides , 1976 .

[45]  G. Gokel,et al.  Stability constants, enthalpies, and entropies for metal ion-lariat ether interactions in methanol solution , 1984 .

[46]  P. Devaux,et al.  Orientation and vertical fluctuations of spin-labeled analogues of cholesterol and androstanol in phospholipid bilayers. , 1987, Biochimica et Biophysica Acta.

[47]  J. Keana,et al.  Azethoxyl nitroxide spin-labeled crown ethers and cryptands with the N-O.bul. group positioned near the cavity , 1983 .

[48]  P. Kuo,et al.  Salt effects on the surface properties of long-chain alkyl substituted crown compounds , 1983 .

[49]  G. Gokel,et al.  N,N'-Bis(subst1tuted)-4,13-diaza-18-crown-6 derivatives having pi-donor-group-sidearms: correlation of thermodynamics and solid state structures , 1988 .

[50]  M. Grätzel,et al.  Surface activity and micelle formation of alkyl-substituted aza-crown ethers and their metal ion complexes , 1979 .

[51]  Merrifield Rb,et al.  Solid-phase synthesis of the cyclododecadepsipeptide valinomycin , 1969 .

[52]  Barry W. Ninham,et al.  Molecular forces in the self-organization of amphiphiles , 1986 .

[53]  H. Schneider,et al.  Cryptate formation in nonaqueous solvents: new aspects in single-ion thermodynamics , 1978 .

[54]  V. J. Gatto,et al.  Novel synthetic access to 15- and 18-membered ring diaza-bibracchial lariat ethers (BiBLEs) and a study of sidearm-macroring cooperativity in cation binding , 1986 .

[55]  A. Florence,et al.  The preparation and properties of niosomes—non‐ionic surfactant vesicles , 1985, The Journal of pharmacy and pharmacology.

[56]  F. Vögtle,et al.  Multidentate Acyclic Neutral Ligands and Their Complexation , 1979 .

[57]  M. Dobler Ionophores and Their Structures , 1981 .

[58]  A. Balch,et al.  Study of Steric Effects by Electron Spin Resonance Spectroscopy and Polarography. Substituted Nitrobenzenes and Nitroanilines , 1964 .

[59]  R. M. Izatt,et al.  Synthetic multidentate macrocyclic compounds , 1978 .

[60]  G. Gokel,et al.  Crown-cation complex effects. 15. Lariat ethers. 4. Chain length and ring size effects in macrocyclic polyethers having neutral donor groups on flexible arms , 1982 .

[61]  M. Truter Structures of organic complexes with alkali metal ions , 1973 .

[62]  Angel E. Kaifer,et al.  Enhanced sodium cation binding by electrochemically reduced nitrobenzene-substituted lariat ethers , 1983 .

[63]  M. Delbruck,et al.  Structural Chemistry and Molecular Biology , 1968 .

[64]  G. Gokel,et al.  Clarification of the hole-size cation-diameter relationship in crown ethers and a new method for determining calcium cation homogeneous equilibrium binding constants , 1983 .

[65]  Peter F. Knowles,et al.  Magnetic Resonance of Biomolecules , 1976 .

[66]  G. Gokel,et al.  Phase Transfer Catalysis in Organic Synthesis , 1977 .

[67]  V. J. Gatto,et al.  Evidence for cryptand-like behavior in bibracchial lariat ether (BiBLE) complexes obtained from X-ray crystallography and solution thermodynamic studies , 1987 .

[68]  V. J. Gatto,et al.  Syntheses and binding properties of bibrachial lariat ethers (BiBLEs): survey of synthetic methods and cation selectivities , 1986 .

[69]  G. Gokel,et al.  Lariat ethers. 2. The remarkable solvent dependence of binding constants in macrocyclic polyethers bearing secondary donor groups on flexible arms , 1981 .

[70]  P. Nordio,et al.  2 – General Magnetic Resonance Theory , 1976 .

[71]  D. Reinhoudt,et al.  Crown ether mediated transport: a kinetic study of potassium perchlorate transport through a supported liquid membrane containing dibenzo-18-crown-6 , 1987 .

[72]  R. Hornreich,et al.  Landau theory of twist-induced biaxiality in cholesteric liquid crystals , 1984 .

[73]  M. J. Weaver,et al.  The thallium(I)/thallium amalgam couple as an electrochemical probe of cryptate thermodynamics in non-aqueous solvents , 1979 .

[74]  S. Kulstad,et al.  Diaza-crown ethers—II , 1980 .

[75]  J. D. Lamb,et al.  Thermodynamic and kinetic data for cation-macrocycle interaction , 1985 .

[76]  W. Hubbell,et al.  Molecular motion in spin-labeled phospholipids and membranes. , 1971, Journal of the American Chemical Society.

[77]  G. Gokel,et al.  12-, 15-, and 18-membered-ring nitrogen-pivot lariat ethers: syntheses, properties, and sodium and ammonium cation binding properties , 1985 .

[78]  D. F. Evans,et al.  Structural changes in sodium dodecyl sulfate micelles induced by using counterion complexation by macrocyclic ligands , 1986 .

[79]  V. J. Gatto,et al.  Enhanced transport of Li+ through an organic model membrane by an electrochemically reduced anthraquinone podand , 1986 .

[80]  Tetsuya Nakamura,et al.  Molecular design of the electron-donating sidearm of lariat ethers: effective coordination of the quinoline moiety in complexation toward alkali-metal cations , 1988 .

[81]  A. I. Popov,et al.  Sodium-23, cesium-133 and thallium-205 NMR study of sodium, cesium and thallium complexes with large crown ethers in nonaqueous solutions , 1980 .

[82]  R. D. Shannon Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[83]  A. Kaifer,et al.  Cryptand 222 complexation of anionic surfactant counterions. Drastic decrease of the critical micelle concentration of sodium dodecyl and sodium decyl sulfates , 1987 .

[84]  G. Gokel,et al.  Aggregation of steroidal lariat ethers: the first example of nonionic liposomes (niosomes) formed from neutral crown ether compounds , 1988 .

[85]  J. Reisse,et al.  Solution thermodynamic studies. Part 6. Enthalpy-entropy compensation for the complexation reactions of some crown ethers with alkaline cations: a quantitative interpretation of the complexing properties of 18-crown-6 , 1982 .

[86]  J. Seelig Spin label studies of oriented smectic liquid crystals (a model system for bilayer membranes) , 1970 .

[87]  G. Gokel,et al.  Electrochemical switching in reducible lariat ethers: From cation binding enhancements to electrochemically-mediated transport , 1989 .

[88]  N. Purdie,et al.  Dynamics of a conformational change in aqueous 18‐crown‐6 by an ultrasonic absorption method , 1978 .

[89]  D. A. Gustowski,et al.  Electrochemical switching in anthraquinone-substituted carbon-pivot lariat ethers and podands: chain length effects in geometric and electronic cooperativity. , 1986, Journal of the American Chemical Society.