Tuneable enhancement of the salt and thermal stability of polymeric micelles by cyclized amphiphiles

Honda, Satoshi; Yamamoto, Takuya; Tezuka, Yasuyuki

doi:10.1038/ncomms2585

Cited by 157 publications

(178 citation statements)

References 55 publications

(76 reference statements)

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“…For instance, recent studies demonstrated that thermal stability of polymer micelles increased drastically by a linear-to-cyclic conversion. 7,8 Simulation studies have also suggested an essential role of a loop formation of DNA in a spatial organization of chromosomes. [9][10][11][12][13] These studies point to the critical roles of the cyclization of the polymer chains in various research fields, from materials science to life science.…”

Section: Introductionmentioning

confidence: 99%

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

2015

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that the method provides an invaluable tool for characterizing topological interaction between the entangled chains. We further demonstrate that the current models proposed for the entanglement between cyclic polymers which are based on cyclic chains moving through an array of fixed obstacles cannot correctly describe the motion of the cyclic chain under the entangled conditions.Our results rather suggest the mutual relaxation of the cyclic chains, which underscore the necessity of developing a new model to describe the motion of cyclic polymer under the entangled conditions based on the mutual interaction of the chains.3

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Section: Introductionmentioning

confidence: 99%

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

2015

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“…Thus, in the case of LB multilayers, the heat resistance properties of the cyclic polymers were indicated as reported in previous study. 3,4) The excellent heat stability 13) of cyclic polymers was demonstrated. Based on the results of temperature-controlled out-of-plane XRD, fig.7 shows the disordering behavior of polymers in LB multilayers with heating.…”

Section: Molecular Arrangement Of Organized Molecular Films Of Linearmentioning

confidence: 99%

“…3,4) In this study, the effect on the formation of interfacial molecular films was noted when amphiphilic polymers with different "shape" have been spread to the air/water interface. The merit of this material evaluation in this viewpoint is the fact that components of cell membranes of all including a human corresponds to a linear lipid molecule.…”

Section: Introductionmentioning

confidence: 99%

Molecular Arrangement of Organized Molecular Films of Linear and Cyclic Amphiphilic Block Copolymers with Different Shapes

Hashimoto

Honda

et al. 2014

Trans. Mat. Res. Soc. Japan

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A "topological polymer chemistry" as a new concept in polymer science at the air/water interface is investigated by using amphiphilic linear and cyclic block copolymers consisting of butyl acrylate and ethylene oxide. The relatively stable monolayers of these two kinds of amphiphilic copolymers were formed at the air/water interface. In addition, these two kinds of amphiphilic copolymers constructed highly ordered Langmuir-Blodgett (LB) multilayers. In order to estimate the layered regularity under high temperature, the temperature-controlled out-of-plane X-ray diffraction (XRD) of LB films of amphiphilic linear and cyclic block copolymers was obtained. As a result, excellent heat-resistant propertyies of organized molecular films of the cyclic copolymer were confirmed. At room temperature, both copolymers showed clear diffraction peaks based on the formation of highly ordered layer structures. However, in the case of linear copolymers, layered structures were gradually disordered with heating. On the other hand, regularity of LB multilayers of the cyclic copolymers did not change with heating up to 50 °C. In this case, higher order reflections (d 002 , d 003 ) of XRD are also unchanged, which means the formation of highly ordered regularity.

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“…In comparison with linear polymers,c orresponding topological polymers, [2] such as star polymers, [3] cyclic polymers, [4] dendrimers, [5] and hyperbranched polymers, [6] generally provide smaller hydrodynamic volume,l ower solution viscosity,a nd less polymer entanglement in the bulk. These properties are useful in solid materials that can help not only in reducing solvent use as sustainable products but also making the molding process easy because of low melt viscosity.…”

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confidence: 99%

Star/Linear Polymer Topology Transformation Facilitated by Mechanical Linking of Polymer Chains

2015

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Topology transformation of as tar polymer to al inear polymer is demonstrated for the first time.Athreearmed star polymer possessing am echanical linking of two polymer chains was synthesized by the living ring-opening polymerization of d-valerolactone initiated by ap seudo [2]rotaxane having three hydroxy groups as the initiator sites on the wheel component and at both axle termini. The polymerization was followed by the propagation end-capping reaction with ab ulky isocyanate not only to prevent the wheel component deslippage but also to introduce the urethane moiety at the axle terminal. The resulting rotaxane-linked star polymer with afixedrotaxane linkage based on the ammonium/crown ether interaction was subjected to N-acetylation of the ammonium moiety,which liberated the components from the interaction to movet he wheel component to the urethane terminal as the interaction site,e ventually affording the linear polymer.T he physical property change caused by the present topology transformation was confirmed by the hydrodynamic volume and viscosity.Structure or topology transformation and the resulting property change often seen in molecular switches or machines have attracted much attention because of their potential applicability to the macroscopic change of appearance or properties.[1] Because such atransformation is mainly limited to small molecules,atopology-transformable polymer would be attractive for bulk property control. In comparison with linear polymers,c orresponding topological polymers, [2] such as star polymers, [3] cyclic polymers, [4] dendrimers, [5] and hyperbranched polymers, [6] generally provide smaller hydrodynamic volume,l ower solution viscosity,a nd less polymer entanglement in the bulk. These properties are useful in solid materials that can help not only in reducing solvent use as sustainable products but also making the molding process easy because of low melt viscosity.However,m ost topological polymers [7] reported to date are not transformable,b ecause they are constructed by covalent bonds.T here are af ew reports on topology reconstruction using weak and reversible interactions to change polymer properties.[8] Meanwhile,w eh ave recently reported [9] the synthesis of mechanically linked block/graft copolymers as as hape-transformable polymer in which the two polymer chains are tied by the rotaxane structure;o ne polymer chain is threaded into the crown ether wheel to which the other is connected. Because we have found that the urethane moiety placed in the rotaxane axle has some attractive interaction with the crown ether wheel, [9c] which is consistent with Gibsons reports, [10] crown ether based rotaxanes having both ammonium and urethane moieties can be regarded as two-station-type molecular switches.Namely,the rotaxane structure plays akey role as acontrollable movable linking unit, thereby being applicable to more sophisticated transformable systems.T his paper describes the synthesis of as tar polymer characterized by the rotaxane linking of the polymer ch...

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Tuneable enhancement of the salt and thermal stability of polymeric micelles by cyclized amphiphiles

Cited by 157 publications

References 55 publications

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

Molecular Arrangement of Organized Molecular Films of Linear and Cyclic Amphiphilic Block Copolymers with Different Shapes

Star/Linear Polymer Topology Transformation Facilitated by Mechanical Linking of Polymer Chains

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