High Conversion Synthesis of Pyrene End Functionalized Polyrotaxane Based on Poly(ethylene oxide) and α-Cyclodextrins

Jarroux, Nathalie; Guégan, Philippe; Cheradame, Hervé; Auvray, L.

doi:10.1021/jp054908t

Cited by 61 publications

(90 citation statements)

References 20 publications

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“…As shown in Table 1, 72% of the PEG chains is covered by CDs in DNFB-PR2000 and probably also in APR2000, whereas the inclusion ratios of DNFB-PR3350 and APR35000 are 52% and 25-30%, respectively. Since the polyrotaxane molecules with a high inclusion of CDs are known to become rigid [36,37], DNFB-PR2000 and APR2000 molecules possess the most rigid molecular conformation and relatively large excluded volume among the samples in the present study, resulting in the facile formation of a three-dimensional network when contacted via intermolecular hydrogen bonding in DMSO. A more detailed investigation on the persistence lengths of these polyrotaxanes (for example, with static light scattering measurements) might be performed, although it seems to be problematical due to the abovementioned aggregation only below a polyrotaxane concentration of 1% and gelation at a concentration of 2.5%.…”

Section: Resultsmentioning

confidence: 98%

Strongly thixotropic viscosity behavior of dimethylsulfoxide solution of polyrotaxane comprising α-cyclodextrin and low molecular weight poly(ethylene glycol)

Araki

Ito

2007

Polymer

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A strong thixotropic viscosity behavior was observed when polyrotaxane prepared from α-cyclodextrins (CDs) and poly(ethylene glycol) (PEG) with a molecular weight of 2000 was dissolved in dimethylsulfoxide (DMSO). A 10 wt% solution liquefied by vigorous shaking was rapidly gelated by standing --this sol-gel transition was reversible. The time for recovering the viscosity was dependent on the polyrotaxane concentration, i.e., a 10wt% solution regelated within 30 s, whereas several hours were required for the gelation of a 2.5wt% solution. The thixotropic nature of the solution was also confirmed by the clockwise hysteresis curve of the viscosity when the shear rate was increased and decreased. The gel permeation chromatography (GPC) measurement of the polyrotaxane in DMSO exhibited peaks in the high molecular weight region. The peak disappeared after the phenylcarbamoylation of polyrotaxane, suggesting that the peak was due to loose aggregations of polyrotaxane in DMSO. On the other hand, the DMSO solution of polyrotaxane prepared from CD and PEG with a molecular weight of 3350-whose inclusion ratio (51%) is slightly lower than that of PEG2000 polyrotaxane (72%)-neither demonstrated the abovementioned thixotropic viscosity nor the peak corresponding to the aggregations occurring during the GPC measurement. The thixotropic behavior was speculated to be caused by the combined contribution of intermolecular attractive hydrogen bonding and higher rigidity of polyrotaxane prepared from PEG 2000 than that of polyrotaxane prepared from PEG3350, presumably due to the higher inclusion ratio of the former than that of the latter. Key Word: Polyrotaxane, Thixotropy, intermolecular hydrogen bonding 2 INTRODUCTIONPolyrotaxane is a typical supramolecular material that possesses linear molecule threading through many cyclic molecules, which can freely slide or rotate over the linear molecule [1][2][3][4]. Great advances have been made in the investigation of polyrotaxane since the discovery of the formation of pseudopolyrotaxane by the spontaneous inclusion complexation of cyclodextrins (CDs) and linear polymers by Harada et al. [5][6][7][8][9]. The formation of the inclusion complex with CDs and various linear polymers via spontaneous self-assembly was thoroughly investigated by Harada et al. [1,5,6], who successfully prepared polyrotaxane by binding bulky end groups (such as dinitrophenyl moieties) to the ends of pseudopolyrotaxane, i.e., the inclusion complex of CDs and PEG [7][8][9]. A wide variety of attractive concepts have been reported to date after the first finding by Harada, such as the preparation of a "molecular tube" by cross-linking adjacent CDs in single polyrotaxane followed by the dissociation of the included PEG [10], an insulated molecular wire comprising a conducting polymer and a molecular tube [11,12], a drug delivery system using polyrotaxane carrying drugs on the CD moiety [13], multivalent ligand system [14], the construction of an energy transfer system using polyrotaxane with photoluminescent...

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Section: Resultsmentioning

confidence: 98%

Strongly thixotropic viscosity behavior of dimethylsulfoxide solution of polyrotaxane comprising α-cyclodextrin and low molecular weight poly(ethylene glycol)

Araki

Ito

2007

Polymer

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“…less, it can be seen that the usual peak of PEG at 3.40-3.50 ppm in DMSO-d 6 was shifted upfield compared with the case of the blank triblock copolymer without adding a-CDs, ascribed to restricted mobility of the polymer chain inside the molecular tube formed by the cyclodextrin rings. 37 It clearly indicated that the target PRs had been successfully synthesized via the ATRP of HPMA in aqueous media.…”

Section: Atrp Of Hpma Initiated With Pprs Comprising Brib-f127-ibbr Amentioning

confidence: 96%

Novel main‐chain polyrotaxanes synthesized via ATRP of HPMA in aqueous media

Zhang

Zhu

Tong

et al. 2008

J. Polym. Sci. A Polym. Chem.

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“…The aim of this work is to optimize a grafting reaction of large groups on PEO chain ends which could be applied to the synthesis of polyrotaxane starting from a pseudopolyrotaxane containing PEO. [11] The blocking of the cyclic moieties of such a macromolecular assembly by large groups preventing polymer dethreading by steric hindrance is a challenge. To improve the yield of the polyrotaxane synthesis, the grafting reaction must be fast enough to prevent dethreading.…”

Section: Introductionmentioning

confidence: 99%

A New Versatile Radical Addition on α, ω‐Dimethacrylate Poly(ethylene oxide)

Jarroux¹,

Guégan²,

Buchmann³

et al. 2004

Macro Chemistry & Physics

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Summary: The synthesis of α,ω‐di(2‐methyl‐6‐pyrenyl‐2‐succinimidylhexanoic ester)poly(ethylene oxide) (Py(S)‐EOn‐(S)Py) was obtained by a new radical reaction between 4‐pyrenylbutanoate N‐hydroxysuccinimidyl ester and α,ω‐dimethacrylate poly(ethylene oxide). The reason for the choice of such bulky groups is a possible application of this reaction to the synthesis of polyrotaxane from polypseudorotaxane. Two reaction media were examined, heterogeneous in water at room temperature using persulfate as initiator, or homogeneous in DMSO at 60 °C using AIBN as initiator. Structural characterization of the functionalization products was carried out by SEC, MALDI TOF, and NMR spectroscopies. It was shown that two types of α,ω‐dipyrenyl PEO could be obtained, one corresponding to the expected product (Py(S)‐EOn‐(S)Py), the other corresponding to the same structure but without the succinimidyl substituent (Py(H)‐EOn‐(H)Py). It was also shown that in the soluble system macrocycles could be formed and this last aspect has been assigned to intramolecular interactions existing between the pyrenyl groups. An interesting aspect of this synthesis is the possibility to find conditions giving high yields without crosslinking and fairly reduced amount of coupling. magnified image

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High Conversion Synthesis of Pyrene End Functionalized Polyrotaxane Based on Poly(ethylene oxide) and α-Cyclodextrins

Cited by 61 publications

References 20 publications

Strongly thixotropic viscosity behavior of dimethylsulfoxide solution of polyrotaxane comprising α-cyclodextrin and low molecular weight poly(ethylene glycol)

Strongly thixotropic viscosity behavior of dimethylsulfoxide solution of polyrotaxane comprising α-cyclodextrin and low molecular weight poly(ethylene glycol)

Novel main‐chain polyrotaxanes synthesized via ATRP of HPMA in aqueous media

A New Versatile Radical Addition on α, ω‐Dimethacrylate Poly(ethylene oxide)

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