Assembly of Hybrid Synthetic Capsules

Ajami, Dariush; Schramm, Michael; Volonterio, Alessandro; Rebek, Julius

doi:10.1002/anie.200603421

Cited by 49 publications

(77 citation statements)

References 31 publications

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“…Calixarene-based capsules are a topic of numerous reports; so dimeric capsules [1][2][3][4][5] as well as species of higher multiplicity [6][7][8][9] are intensively studied due to their interesting properties and application possibilities. Calixarene-based capsules of higher multiplicity are mainly trimeric and hexameric species, albeit tetrameric and octameric compounds are also known.…”

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confidence: 99%

Trimeric and hexameric calixarene-based capsules

Śliwa¹,

Dondela²

2007

Arkivoc

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Section: Introductionmentioning

confidence: 99%

Trimeric and hexameric calixarene-based capsules

Śliwa¹,

Dondela²

2007

Arkivoc

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“…The values shown in Fig. 4 reveal that the lowest changes in Gibbs energies belong to the formation of 8a and to those of the 'mixed' compounds (11)(12)(13)(14). In contrast, 6a…”

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“…In addition to the geometry optimizations, thermodynamic calculations were also carried out to obtain the changes of enthalpy, entropy and Gibbs energy associated to reactions starting from the same compounds but forming different products at 298 K, both in vacuum and in DMF solvent (COSMO model), as shown in the Supporting Information (Tables S2 and S3). The changes in the Gibbs energies (Δ f G) for the carbonylation reactions affording 'pure' (6a, 8a) and 'mixed' (11)(12)(13)(14) products are shown in Figure 4 (see also Table S4). The variations in the Gibbs energies associated to the formation of these carboxamidocavitands were calculated according to equations (1-4):…”

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Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic Self-Sorting on a Cavitand Platform

et al. 2016

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Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic SelfSorting on a Cavitand Platform http://researchonline.ljmu.ac.uk/5117/ Article LJMU has developed LJMU Research Online for users to access the research output of the University more effectively. Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Users may download and/or print one copy of any article(s) in LJMU Research Online to facilitate their private study or for non-commercial research. You may not engage in further distribution of the material or use it for any profit-making activities or any commercial gain.The version presented here may differ from the published version or from the version of the record. Please see the repository URL above for details on accessing the published version and note that access may require a subscription. self-sorting. The reactivity order of the amine reactants and the changes in the Gibbs energies calculated using the semiempirical PM6 model suggest that this self-sorting process is kinetically controlled.

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“…A number of longer alkanes were encapsulated in this host assembly, but the expanded capsule also offered broadened possibilities for isomerism and accommodated other guests that we elaborate on here. The results indicate that highly complex molecular assemblies can emerge from only a few modules acting as hosts and guests (20,21). …”

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Adaptations of guest and host in expanded self-assembled capsules

Ajami

Rebek

2007

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

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Reversible encapsulation complexes create spaces where two or more molecules can be temporarily isolated. When the mobility of encapsulated molecules is restricted, different arrangements in space are possible, and new forms of isomerism (''social isomerism'') are created: the orientation of one encapsulated molecule influences that of the other in the confined space. Expansion of a capsule's length is possible through addition of small-molecule spacer elements. The expanded capsules have dimensions that permit the observation of social isomerism of two identical guests, and they adopt arrangements that properly fill the host's space. The host also can adapt to longer guests by incorporating additional spacers, much as protein modules are added to a viral capsid in response to larger genomes. Arachidonic and related fatty acid derivatives act in this way to induce the assembly of further extended capsules having sufficient length to accommodate them.encapsulation ͉ self-assembly ͉ social isomers E ncapsulation complexes are synthetic, self-assembled hosts that more or less completely surround their guest molecules. They are dynamic and form reversibly in solution with lifetimes ranging from milliseconds to days. The capsules isolate molecules from the bulk solution, and they reveal behaviors that cannot be seen otherwise. They have become a tool of modern physical organic chemistry (1). For example, cylindrical host 1.1 (Fig. 1) self-assembles only in the presence of suitable guests to give encapsulation complexes (2-4). Combinations of different guests (5) inside this capsule have allowed its use as a reaction chamber (6), a chiral receptor (7), and a space where singlemolecule solvation can be observed (8). Elsewhere, reversible encapsulation complexes have been used to stabilize reactive intermediates (9, 10) and even transition states (11, 12) as well as to alter the course of reactions in the limited quarters (13). New forms of stereochemistry also have emerged from coencapsulation studies (14). For example, with benzene and p-ethyl toluene, two complexes coexist (Fig. 1). The two molecules are too large to slip past each other, and the p-ethyl toluene is too long to tumble freely while inside the capsule. Either of these motions could interconvert the complexes, but they are slow on the NMR time scale and separate spectra are seen for the two isomers. These ''social isomers'' are different arrangements in space that arise from the interactions of at least two encapsulated molecules. They also are constitutional isomers, but mechanical barriers hold these arrays in place rather than covalent bond ''connectedness.'' Accordingly, the term supramolecular diastereomers better describes the relationships. This stereoisomerism is related to the carceroisomerism (15) observed in covalently bound capsules with one guest.The self-assembly of the benzene/p-ethyl toluene pair owes its stability to the optimal filling of the capsule's space. Two benzene molecules can assemble the capsule as guests in that solvent and f...

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Assembly of Hybrid Synthetic Capsules

Cited by 49 publications

References 31 publications

Trimeric and hexameric calixarene-based capsules

Trimeric and hexameric calixarene-based capsules

Palladium-Mediated Catalysis Leads to Intramolecular Narcissistic Self-Sorting on a Cavitand Platform

Adaptations of guest and host in expanded self-assembled capsules

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