Switching from <i>altro</i>-α-Cyclodextrin Dimer to <i>pseudo</i>[1]Rotaxane Dimer through Tumbling

Yamauchi, Kazuhiro; Miyawaki, Atsuhisa; Takashima, Yoshinori; Yamaguchi, Hiroyasu; Harada, Akira

doi:10.1021/ol1001736

Cited by 53 publications

(30 citation statements)

References 19 publications

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“…Previously, we have reported that an alkyl altro-a-CD dimer is converted into a pseudo [1]rotaxane dimer through tumbling of the altropyranose unit of altro-a-CD in D 2 O. 40,41 On the basis of these results, PDIC 7 -3bCD 2 forms a pseudo [1]rotaxane dimer through tumbling of the altropyranose unit of altro-b-CD in aqueous solutions (Scheme 1). PDIC 7 -3aCD 2 forms a pseudo [1]rotaxane dimer, which includes the C7 alkyl unit in the altro-a-CD cavity (Scheme 2).…”

Section: Resultsmentioning

confidence: 91%

“…39 Herein we report the selective emission properties of PDI-CD 2 derivatives through the tumbling of the altropyranose unit in an aqueous solution. Previously, we have reported the formation of pseudo [1]rotaxane dimer from the altro-a-CD (altro-a-CD) dimer via tumbling of altro-a-CD, 40,41 which consists of one altropyranose unit and five glucopyranose units. Although some research groups have reported the tumbling of permethylated glucopyranose type CD, [42][43][44][45][46][47] tumbling of the altropyranose unit in altro-CDs has yet to be reported.…”

Section: Introductionmentioning

confidence: 99%

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Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

Takashima

Otsubo

et al. 2012

Polym J

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Perylene diimide (PDI) derivatives with cyclodextrins (PDI-CD 2 s) exhibit specific emission properties, which depend on the type of CDs in an aqueous solution. Herein we successfully create an emission film-kneaded PDI-CD 2 derivatives via effective tumbling of the altropyranose unit. PDI-6CD 2 s are crosslinked with PDI between 6-amino-CDs. Although the emission intensities of PDI-6CD 2 s in dimethyl sulfoxide are similar regardless of the type of CD, PDI-6cCD 2 has a relatively high emission intensity in aqueous solutions. In contrast, for PDIC 7 -3CD 2 s, which are linked with N,N'-bis(6-carboxylhexyl)perylene-3,4,9,10-tetracarboxyl diimide (BisC 7 -PDI) between 3-amino-CDs, the emission intensity of PDIC 7 -3bCD 2 is stronger than those of PDIC 7 -3aCD 2 , PDIC 7 -3cCD 2 , and PDI-6CD 2 s in aqueous solutions. The selective emission behavior of PDIC 7 -3CD 2 s is due to the formation of the pseudo[1]rotaxane dimer through tumbling of the altropyranose unit in an aqueous solution. PDIC 7 -3bCD 2 in the solid state does not demonstrate a distinctive emission due to self-quenching, whereas PDIC 7 -3bCD 2 kneaded into the polyvinyl alcohol (PVA) film exhibits a bright yellow emission. The order of the emission intensities of PDIC 7 -3CD 2 s kneaded into PVA films is similar to those in aqueous solutions. INTRODUCTIONRecently, supramolecular assemblies with extended aromatic compounds have attracted much attention. 1-4 Perylene diimides (PDIs) derivatives effectively form supramolecular assemblies through p-p stacking interaction. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] In particular, supramolecular assemblies based on calixarenePDI conjugates show efficient energy and electron transfer properties due to the well-defined rigid and electron-rich scaffolds of calixarenes. [22][23][24][25][26][27] We have prepared PDI derivatives with a high emission property in aqueous solutions.Generally, PDI derivatives have low solubilities in aqueous solutions. Even if PDI derivatives are dissolved in aqueous solutions by introducing a hydrophilic group, the emission of PDI derivatives exhibit self-quenching in aqueous solutions due to the formation of supramolecular assemblies and folders. To create water-soluble and effective emission sensor materials with PDI derivatives, we have introduced CDs into the PDI motif. The CDs are a family of macrocyclic oligosaccharides; the most common are composed of 6 (a), 7 (b), or 8 (g) a-1,4-linked D-glucopyranose units. [28][29][30][31][32][33][34] The introduction of CDs should influence the molecular recognition property and increase the emission intensity. Although supramolecular assemblies based on permethylated CDPDI conjugates have been previously reported, 35-38 the formation of assemblies cannot prevent the decrease in the monomer emission intensity of the PDI units due

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Section: Resultsmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

Takashima

Otsubo

et al. 2012

Polym J

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“…The two isomeric forms of the chair conformation of the altropyranose unit, that is 1 C 4 and 4 C 1 , correspond to values of 3 approximately equal to +60 and À60 , while the boat-like intermediate approximately corresponds to a value of 3 of 0 . 17,18 Furthermore, as can be seen in Fig. As can be seen in Fig.…”

Section: Conformational Transition Of the Altropyranose Unitmentioning

confidence: 73%

“…Moreover, Harada et al 18 synthesized an altro-a-CD dimer with two C10 linkers and a viologen unit (see Fig. 1B).…”

Section: Introductionmentioning

confidence: 99%

What causes tumbling of altro-α-CD derivatives? Insight from computer simulations

et al. 2015

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In water, a remarkable motion can be observed with a [2]rotaxane, wherein the rotor translocates by reeling its axle in the cavity of an altro-a-CD stopper. Similarly, in aqueous solution, an alkyl altro-a-CD dimer reels its alkyl chain in the altro-a-CD cavity to form a pseudo[1]rotaxane dimer. This reeling motion is in fact induced by the tumbling of the altropyranose unit of an altro-a-CD, a process shown to be solventdependent. Tumbling, however, does not occur in low-polarity solvents such as methanol and DMSO. In the present contribution, the mechanism that underlies solvent-controlled tumbling has been studied at the atomic level by means of molecular dynamics simulations combined with microsecond-timescale free-energy calculations. The free-energy profile delineating the tumbling in water of the altropyranose unit of an alkyl altro-a-CD indicates that a 19.8 kcal mol À1 barrier must be overcome to yield the selfinclusion complex, which is the most stable state available to the supramolecular assembly. In DMSO, the free-energy barrier is about 21.0 kcal mol À1 higher, and the self-included alkyl altro-a-CD corresponds to a metastable state. These results provide new thermodynamic and kinetic insights into solvent-controlled tumbling, and reveal the essence of different experimental observations. Further investigation shows that aside from the polarity of the solvent, tumbling of the altro-a-CD derivative stems from the hydrophobicity of the side chain and the propensity of the former to include the latter, which opens perspectives for the design of new, related supramolecular assemblies.

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“…Furthermore,c ompetitive self-inclusion of the appended hydrophobic group and/or the possibility of forming head-to-head dimers are detrimental to the formation of SMPs.E ven when these competitive complexes are not formed, the degree of polymerization (DP) of CD-based SMPs is rather low.This is linked to the low affinity of guests typically used in the studies and to the relatively low water solubility of the CD monomers. It can occur with aflexible chain attached to the CD rim, [28] but also with amore rigid one such as at riazol [29] or ap henyl ring. [26] We have recently synthesized such amolecule,but, although the adamantane is too large to penetrate the CD cavity from the upper rim, the CD-adamantane conjugate was shown to exist in solution exclusively as aself-included species.…”

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confidence: 99%

Bridging β‐Cyclodextrin Prevents Self‐Inclusion, Promotes Supramolecular Polymerization, and Promotes Cooperative Interaction with Nucleic Acids

et al. 2018

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Dedicated to Professor Pierre Sinaþ on the occasion of his 80th birthday It is still ag reat challenge to imitate naturesa bility to form cooperative self-assembled structures using entirely artificial molecular tools and to confer them with properties.Here we show that cyclodextrins bridged by an ammonium linker with ah ydrophobic substituent efficiently form supramolecular polymers at millimolar concentrations and avoid the competing self-inclusion and head-to-head processes.N otably,s uch assembly can occur at micromolecular concentrations in the presence of genomic DNA, thereby resulting in an efficient compaction of DNAt hat is reversible upon addition of ac ompetitive guest and demonstrating their highly cooperative interaction. We finally show that the supramolecular polymer also cooperatively interacts with siRNAa nd allows its transfection.Cooperative self-assembly [1][2][3] is ap owerful tool to construct elaborate architectures in ab ottom-up approach. For example,n ature heavily relies on cooperativity to build the highly complex components of organisms from smaller units. [4] As imple archetypical example of such constructs is the tobacco mosaic virus (TMV), which is formed from only two cooperatively interacting partners:acoat protein and an ucleic acid (NA) template.T he principle feature of the complex assembly process is that the coat protein assembles only in small entities unless the NA is present and induces its full coverage in ah ighly cooperative manner.I nr everse, Supportinginformation and the ORCID identification number for some of the authors of this article can be found under: https://doi.

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Switching from altro-α-Cyclodextrin Dimer to pseudo[1]Rotaxane Dimer through Tumbling

Cited by 53 publications

References 19 publications

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

What causes tumbling of altro-α-CD derivatives? Insight from computer simulations

Bridging β‐Cyclodextrin Prevents Self‐Inclusion, Promotes Supramolecular Polymerization, and Promotes Cooperative Interaction with Nucleic Acids

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