Ring‐opening polymerization of lipoic acid and characterization of the polymer

Thermal polymerization of DL-α-lipoic acid (LPA) in bulk without any initiator proceeded easily above the melting point of LPA. The molecular weight polymer determined by GPC was high. From the 1H NMR spectra of polymers, poly(LPA) obtained from polymerization of high purity LPA was to consist of cyclic structures, which was confirmed by ESI-MS. Interlocked polymer consisting of poly(LPA) and dibenzo-30-crown-10 entangled with each other was synthesized by the polymerization of LPA in the presence of dibenzo-30-crown-10. From the DSC analysis of the polymers, glass transition temperature was estimated to be about −11 °C, but melting point was not observed, indicating that poly(LPA) is an amorphous polymer. By photodecomposition of poly(LPA), Mn was rapidly decreased at the early stage of the decomposition. After that, the Mn of the polymer kept and then was almost constant even for a prolonged reaction time. On the basis of the results, it would be presumed that poly (LPA) obtained form polymerization of high purity LPA includes an interlocked structure. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

[1]  Wing Yan Chan,et al.  Synthesis of a molecular charm bracelet via click cyclization and olefin metathesis clipping. , 2010, Journal of the American Chemical Society.

[2]  M. Asakawa,et al.  Effective Synthesis of Polymer Catenanes by Cooperative Electrostatic/Hydrogen-Bonding Self-Assembly and Covalent Fixation , 2010 .

[3]  M. Schappacher,et al.  Imaging of catenated, figure-of-eight, and trefoil knot polymer rings. , 2009, Angewandte Chemie.

[4]  A. Kisanuki,et al.  Ring-Opening Polymerization of Aromatic 6-Membered Cyclic Disulfide and Characterization of the Polymer , 2009 .

[5]  K. Endo.  Synthesis and Properties of Cyclic Polymers , 2008 .

[6]  Jong-Mok Kim,et al.  Biomedical Applications of Cyclodextrin Based Polyrotaxanes , 2007 .

[7]  Bao-hang Han,et al.  Cyclodextrin rotaxanes and polyrotaxanes. , 2006, Chemical reviews.

[8]  Feihe Huang,et al.  Polypseudorotaxanes and polyrotaxanes , 2005 .

[9]  Igor L. Medintz,et al.  Synthesis of compact multidentate ligands to prepare stable hydrophilic quantum dot fluorophores. , 2005, Journal of the American Chemical Society.

[10]  Hong Wang,et al.  Polyamide Pseudorotaxanes, Rotaxanes, and Catenanes Based on Bis(5-carboxy-1,3-phenylene)-(3x+2)-crown-x Ethers , 2004 .

[11]  N. Murata,et al.  Synthesis and Characterization of Poly(1,2-dithiane) , 2004 .

[12]  R. Grubbs,et al.  Synthesis of cyclic polybutadiene via ring-opening metathesis polymerization: the importance of removing trace linear contaminants. , 2003, Journal of the American Chemical Society.

[13]  Y. Tezuka,et al.  Metathesis Polymer Cyclization with Telechelic Poly(THF) Having Allyl Groups , 2002 .

[14]  R. Grubbs,et al.  An "Endless" Route to Cyclic Polymers , 2002, Science.

[15]  H. Oike,et al.  Topological polymer chemistry , 2002 .

[16]  H. Frielinghaus,et al.  Synthesis and Characterization of Model Cyclic Block Copolymers of Styrene and Butadiene. Comparison of the Aggregation Phenomena in Selective Solvents with Linear Diblock and Triblock Analogues , 2002 .

[17]  H. Oike,et al.  Efficient Synthesis of Cyclic Poly(oxyethylene) by Electrostatic Self-Assembly and Covalent Fixation with Telechelic Precursor Having Cyclic Ammonium Salt Groups , 2002 .

[18]  Hyunjung Lee,et al.  Retention Behavior of Linear and Ring Polystyrene at the Chromatographic Critical Condition , 2002 .

[19]  H. Oike,et al.  Self‐Assembly and Covalent Fixation for Topological Polymer Chemistry , 2001 .

[20]  H. Oike,et al.  Efficient polymer cyclization by electrostatic self-assembly and covalent fixation with telechelic poly(tetrahydrofuran) having cyclic ammonium salt groups , 2001 .

[21]  H. Oike,et al.  Novel synthesis of single- and double-cyclic polystyrenes by electrostatic self-assembly and covalent fixation with telechelics having cyclic ammonium salt groups , 2001 .

[22]  R. Arakawa,et al.  Determination of cyclic structure for polydithiane using electrospray ionization mass spectrometry , 2000 .

[23]  H. Oike,et al.  Designing Unusual Polymer Topologies by Electrostatic Self-Assembly and Covalent Fixation , 2000 .

[24]  T. Hogen-esch,et al.  Enhanced Fluorescence of Macrocyclic Polystyrene , 2000 .

[25]  N. Murata,et al.  Thermal Polymerization of Cyclic Disulfides and Viscoelastic Behavior of the Resulting Polymers. , 2000 .

[26]  Takahide Mizawa,et al.  Synthesis of α‐maleimide‐ω‐dienyl heterotelechelic poly(methyl methacrylate) and its cyclization by the intramolecular Diels–Alder reaction , 2000 .

[27]  H. Ohtani,et al.  Ring Structure of Cyclic Poly(2-vinylpyridine) Proved by Pyrolysis−GC/MS , 1999 .

[28]  Jean-Pierre Sauvage,et al.  Transition Metal-Containing Rotaxanes and Catenanes in Motion: Toward Molecular Machines and Motors , 1998 .

[29]  T. Itoh,et al.  Synthesis of α-Carboxyl, ω-Amino Heterodifunctional Polystyrene and Its Intramolecular Cyclization , 1997 .

[30]  G. Rapenne,et al.  Efficient synthesis of a molecular knot by copper(I)-induced formation of the precursor followed by ruthenium(II)-catalysed ring closing metathesis , 1997 .

[31]  K. Ishizu,et al.  Novel synthesis and characterization of cyclic polystyrenes , 1996 .

[32]  K. Ganesh,et al.  Polymers containing disulfide, tetrasulfide, diselenide and ditelluride linkages in the main chain , 1995 .

[33]  M. Schappacher,et al.  New routes to macrocyclic polymers of controlled dimensions , 1994 .

[34]  M. Schappacher,et al.  A new strategy for the synthesis of cyclic polystyrenes : principle and application , 1994 .

[35]  H. Gibson,et al.  Macrocyclic polymers. 2. Synthesis of poly(amide crown ethers) based on bis(5-carboxy-1,3-phenylene)-32-crown-10. Network formation through threading , 1992 .

[36]  M. Schappacher,et al.  Synthesis of macrocyclic poly(2‐chloroethyl vinyl ether)s , 1991 .

[37]  David J. Williams,et al.  Ein [2]‐Catenan auf Bestellung , 1989 .

[38]  Jean-Pierre Sauvage,et al.  Interlocking of molecular threads: from the statistical approach to the templated synthesis of catenands , 1987 .

[39]  G. Hadziioannou,et al.  Thermodynamic and hydrodynamic properties of dilute solutions of cyclic and linear polystyrenes , 1987 .

[40]  J. Roovers.  The melt properties of ring polystyrenes , 1985 .

[41]  J. Roovers,et al.  Synthesis of high molecular weight ring polystyrenes , 1983 .

[42]  Jean-Pierre Sauvage,et al.  Une nouvelle famille de molecules : les metallo-catenanes , 1983 .

[43]  Jia Huang,et al.  Synthesis and characterization of ring- and catena-polystyrene with high molecular weight by reaction of polystyrene dianions with p-dibromoxylene , 1981 .

[44]  H. Höcker,et al.  Synthesis and Investigation of Macrocyclic Polystyrene , 1980 .

[45]  P. Rempp,et al.  Synthesis of ring-shaped macromolecules , 1980 .

[46]  E. Wasserman,et al.  THE PREPARATION OF INTERLOCKING RINGS: A CATENANE1 , 1960 .

[47]  E. Walton,et al.  Properties and Derivatives of α-Lipoic Acid , 1956 .

[48]  M. Calvin,et al.  The Chemistry of 1,2-Dithiolane (Trimethylene Disulfide) As aModel for the Primary Quantum Conversion Act in Photosynthesis , 1954 .

[49]  G. Dougherty,et al.  THE PREPARATION AND RELATIVE REACTIVITIES OF MANY-MEMBERED CYCLIC DISULFIDES , 1950 .