Formation Process of Cyclodextrin Necklace−Analysis of Hydrogen Bonding on a Molecular Level

Miyake, Koji; Yasuda, Satoshi; Harada, Akira; Sumaoka, Jun; Komiyama, Makoto; Shigekawa, Hidemi

doi:10.1021/ja026224u

Cited by 132 publications

(125 citation statements)

References 19 publications

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“…Thus, as discussed experimentally, 27,48,51 the complex formation is thought to be promoted by hydrogen bonds between CDs units. If the solvent effect is taken into account, a stabilization of hydrophobic nature should favor the filled interaction in comparison to the empty complex.…”

Section: -Cd Ae ( -Cdmentioning

confidence: 85%

“…Similar arguments were previously used by Harada's group, in attempt to explain the existence of 20% of HT conformation among CD associations in "necklaces" formed by the same host-guest system. 27 Despite the dependence of combined interactions requested in the complex formation, a question could be raised: Can the polymeric chain interfere in CD dimer formation, along the pseudo-polyrotaxane self-assembly process?Due to the intrinsic nature of intermolecular interactions that can be established in host-guest compounds, quantum mechanical calculations are recommendable to treat this process in a molecular level. Nonetheless, the large size of the CD precludes the use of computational methods based on high level ab initio molecular orbital theory.…”

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confidence: 99%

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confidence: 99%

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Theoretical study of α-CD based [3] pseudorotaxanes: the role played by threadlike polymer on the stability of Cyclodextrin dimers

Anconi¹,

Nascimento²,

Almeida³

et al. 2008

J. Braz. Chem. Soc.

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As interações entre ciclodextrinas e seus agregados com cadeias poliméricas, têm atraído a atenção de pesquisadores em diferentes subáreas da química supramolecular. Esses compostos, conhecidos como "necklaces", podem ser empregados na formulação de fios e nanotubos moleculares. No presente artigo a formação de dímeros de -CD foi estudada teoricamente considerando as três possíveis orientações relativas, denominadas "head-to-head" (HH), "tail-totail" (TT) e "head-to-tail" (HT). A influência da cadeia polimérica na estabilidade relativa das diferentes associações foi avaliada através do estudo dos compostos de inclusão de ( -CD) 2 com oligo(etilenoglicol) (OEG). Os resultados mostram que a orientação relativa das CDs é definida, primeiramente, pelas interações intermoleculares entre as unidades de -CD, tendo a cadeia polimérica um papel secundário no processo de agregação.Cyclodextrins (CDs) and polymeric chains have attracted considerable attention, being addressed in the literature as novel molecular assembly. The so-called "Molecular Necklace" synthesized by the inclusion of a polymeric chain inside CDs cavity has been employed in the formulation of molecular wires and nanotubes. In this paper we applied our previous reported mixed basis set approach in order to investigate theoretically the -CD inclusion complexes formed by two CD units and an oligo(ethylene glycol) (OEG). In attempt to analyze the role played by the OEG in the formation of pseudo-rotaxane in gas-phase, DFT calculations were performed for six possible dimer associations of CDs, named head-to-head (HH), tail-to-tail (TT) and head-to-tail (HT) with or without an OEG threadlike molecule included in the cavity formed by the -CD dimer. The comparison between relative energies of empty (HH, TT and HT) and filled associations (HH-OEG, TT-OEG and HT-OEG) shows that the OEG chain does not interfere significantly in the relative stabilization energies of the supramolecular systems, therefore the relative arrangements of CDs in the necklace structures should be primarily driven by interactions between cyclodextrin units. Keywords: DFT, alpha cyclodextrin, dimer, OEG, inclusion complex IntroductionCyclodextrin (CD) is a cyclic oligomer of -D-glucose obtained by the action of certain enzymes on starch. Generally described as shallow truncated cones, this class of carbohydrate presents a hydrophobic cavity of different sizes, depending on the number of elementary glucose units. In addition, the structure of the CD molecule possess two different rims, a wider (head) containing all secondary hydroxyl groups and a narrower (tail) containing all primary hydroxyl groups. There are three natural cyclodextrins readily available having six, seven or eight glucose units named -CD, -CD and -CD, respectively.The applications of CDs in supramolecular chemistry have been widely addressed in the literature and the applicability of this class of carbohydrate is closely related to its ability to form inclusion compounds with a very wide range of guest molecules in aqueo...

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Section: -Cd Ae ( -Cdmentioning

confidence: 85%

mentioning

confidence: 99%

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confidence: 99%

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Theoretical study of α-CD based [3] pseudorotaxanes: the role played by threadlike polymer on the stability of Cyclodextrin dimers

Anconi¹,

Nascimento²,

Almeida³

et al. 2008

J. Braz. Chem. Soc.

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“…α-CD is a sixmembered sugar ring that complexes with the PEG chains ( Fig. 1J) (24), adding hydrophobicity and functional moieties (25). PEG hydrogels containing 1% CD promote cell aggregation and clustering (Fig.…”

Section: Iptg Diffuses Through Various Materials and Activates Genetimentioning

confidence: 99%

Regulating synthetic gene networks in 3D materials

Deans

Singh

Gibson

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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Combining synthetic biology and materials science will enable more advanced studies of cellular regulatory processes, in addition to facilitating therapeutic applications of engineered gene networks. One approach is to couple genetic inducers into biomaterials, thereby generating 3D microenvironments that are capable of controlling intrinsic and extrinsic cellular events. Here, we have engineered biomaterials to present the genetic inducer, IPTG, with different modes of activating genetic circuits in vitro and in vivo. Gene circuits were activated in materials with IPTG embedded within the scaffold walls or chemically linked to the matrix. In addition, systemic applications of IPTG were used to induce genetic circuits in cells encapsulated into materials and implanted in vivo. The flexibility of modifying biomaterials with genetic inducers allows for patterned placement of these inducers that can be used to generate distinct patterns of gene expression. Together, these genetically interactive materials can be used to characterize genetic circuits in environments that more closely mimic cells' natural 3D settings, to better explore complex cell-matrix and cell-cell interactions, and to facilitate therapeutic applications of synthetic biology.T he complexity of cell signaling can be simplified by considering genetic networks composed of subsets of simpler parts, or modules. This simplification is the foundation of synthetic biology, where engineering paradigms are applied in rational and systematic ways to produce predictable and robust systems for understanding mechanisms of cellular function (1-6). The majority of work in synthetic biology has been in simple organisms, such as yeast and bacteria. However, as synthetic biology starts to expand to mammalian systems, it becomes increasingly more important to consider the environment in which the cells are grown. Biomaterials will play an important role in advancing synthetic biology within mammalian systems, because they provide highly controllable and tunable microenvironments where cells can behave as they do in vivo, in addition to organizing and delivering therapeutic cells to locations of interest. Our results show that interfacing synthetic biology and biomaterials can catalyze synthetic biology applications through engineered biomaterials that actively control genetic circuits in 3D scaffolds to more closely mimic the cells' natural settings, in addition to providing mechanisms for translating synthetic biology for clinical applications (Fig. S1).Biomaterials provide 3D environments for cell growth and have rapidly advanced our ability to investigate the coordinated interactions of many cellular phenomena because biomaterials recapitulate the in vivo setting better than traditional 2D cultures, where cells are grown in monolayers (7,8). Physiological development, homeostasis, and regeneration each require a complex interplay of multiple signals that originate from the extracellular matrix (ECM) and from the intrinsic cellular control of gene products (9). Wh...

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“…In the case of a linear guest, the resulting complex is referred as a pseudorotaxane, i.e., a stable bimolecular system formed by a linear molecule that is threading the CD 7,8 . Recently, special interest have been showed in the so-called "polyrotaxanes" in which a polymer uses for the creation of new molecular materials 10,11 . However, to our knowledge, no works have been published in which a pseudorotaxane was an intrinsic part of an epoxy-based thermoset.…”

Section: Introductionmentioning

confidence: 99%

Pseudorotaxanes of Cyclodextrin and Diglycidyl Ether of Bisphenol A as Precursors of New Intramolecularly Reinforced Epoxy-based Thermosets

González‐Gaitano

González‐Benito

2008

Supramolecular Chemistry

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Formation Process of Cyclodextrin Necklace−Analysis of Hydrogen Bonding on a Molecular Level

Cited by 132 publications

References 19 publications

Theoretical study of α-CD based [3] pseudorotaxanes: the role played by threadlike polymer on the stability of Cyclodextrin dimers

Theoretical study of α-CD based [3] pseudorotaxanes: the role played by threadlike polymer on the stability of Cyclodextrin dimers

Regulating synthetic gene networks in 3D materials

Pseudorotaxanes of Cyclodextrin and Diglycidyl Ether of Bisphenol A as Precursors of New Intramolecularly Reinforced Epoxy-based Thermosets

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