Supramolecular polymer chemistry: design, synthesis, characterization, and kinetics, thermodynamics, and fidelity of formation of self-assembled dendrimers

Zeng, Fuxing; Zimmerman, Steven C.; Kolotuchin, Sergei; Reichert, David E.; Ma, Yuguo

doi:10.1016/s0040-4020(01)01113-9

Cited by 67 publications

(43 citation statements)

References 53 publications

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“…9) and previously reported hexameric aggregates (13 a-c) 6 and (14a) 6 (16)(17)(18). As shown in Table 1, the polystyrenederived M n values were consistent with formation of hexamer from 7b and 7c [see (7Ј) 6 ] and formation of a dodecamer such as 17 (Fig.…”

Section: Resultssupporting

confidence: 56%

“…Strikingly, two peaks were observed in the SEC traces of 7a in dilute (Ͻ10 Ϫ4 M) THF solutions. One peak corresponded to the same species seen in toluene (e.g., 12-mer), whereas the other had a very high polystyrene-based molecular weight (Ͼ85,000) consistent with formation of polymer (7) n (12,17,23). Another notable feature of the assemblies formed by 7 a-c is their exceptional stability-in particular the hexamer formed from 7c.…”

Section: Resultsmentioning

confidence: 79%

“…Treatment of 6 a-c with 3 gave 7 a-c in moderate yield. The Fréchet-type dendrons (22) solublize the heterocyclic unit, but more importantly allow direct comparison to previously reported self-assembling dendrimers 13 and 14 (16)(17)(18).…”

Section: Resultsmentioning

confidence: 93%

“…We as well as others have shown that size-exclusion chromatography (SEC) using appropriate synthetic size standards can be a powerful method for determining the structure of solution aggregates (2,(16)(17)(18). Thus, the self-assembly of 7 a-c was studied by SEC, with most of the experiments focused on the first-and third-generation dendrons (i.e., 7 a and c).…”

Section: Resultsmentioning

confidence: 99%

“…All compounds described herein gave NMR, matrixassisted laser desorption ionization (MALDI)-time of flight MS, and UV-visible spectra in accord with their structures, and each key compound gave a passing elemental analysis. Compounds 3 (15), 9 a-c (16,17), 10 a-c (16,17), 13 a-c (16,17), 14a (18), 14 b and c (Y.M., S. V. Kolotuchin, and S.C.Z., unpublished work), 15 (16,17), 3,3,3-triphenylpropylamine (19), 6-bromo-5-deazapterin (20), and Gn-Br dendrons a-c (16,17) were prepared by known methods. Size standards 16 a and b were prepared by using the same precursors as for 15 and by analogous methods.…”

Section: Methodsmentioning

confidence: 99%

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Discrete and polymeric self-assembled dendrimers: Hydrogen bond-mediated assembly with high stability and high fidelity

Corbin

Lawless

et al. 2002

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

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170

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Hydrogen bond-mediated self-assembly is a powerful strategy for creating nanoscale structures. However, little is known about the fidelity of assembly processes that must occur when similar and potentially competing hydrogen-bonding motifs are present. Furthermore, there is a continuing need for new modules and strategies that can amplify the relatively weak strength of a hydrogen bond to give more stable assemblies. Herein we report quantitative complexation studies on a ureidodeazapterin-based module revealing an unprecedented stability for dimers of its self-complementary acceptoracceptor-donor-donor (AADD) array. Linking two such units together with a semirigid spacer that carries a first-, second-, or third-generation Fré chet-type dendron affords a ditopic structure programmed to self assemble. The specific structure that is formed depends both on the size of the dendron and the solvent, but all of the assemblies have exceptionally high stability. The largest discrete nanoscale assembly is a hexamer with a molecular mass of about 17.8 kDa. It is stabilized by 30 hydrogen bonds, including six AADD⅐DDAA contacts. The hexamer forms and is indefinitely stable in the presence of a hexamer containing six ADD⅐DAA hydrogen-bonding arrays. A t the most fundamental level, the readout of stored information in biochemical systems requires both a code and the machinery for expressing the code (1). Distinction at the molecular level is critical in such processes and in its simplest form involves a molecular recognition event. The code may be, for example, the primary sequence of a polypeptide, which through a series of recognition events folds into a specific secondary or tertiary structure, or it may be a linear array of recognition sites that are sequentially processed through a distinctive engagement at each site. However, a distinctive chemical process alone (e.g., DNA base pairing) is not sufficient. It must be coupled with a biological process (e.g., replication) to be considered authentic information retrieval.Inspired by nature's ability to create extraordinarily complex systems from comparatively simple information codes, and with an eye toward creating nanoscale devices (2), chemists have sought to develop small molecules capable of self-assembling into larger structures (3-10). Molecular recognition sites within these small molecules carry the code that guide the assembly. Thus, the information retrieval process is expressed through the formation of the self-assembled structure, which can further manifest itself through the bulk properties of the material formed (11,12). Despite the many successful examples that have appeared over the past decade, the power of this biomimetic self-assembly strategy has not been fully realized largely because of the limited number of recognition motifs available, and, in particular, their relatively low stability (4, 13). Moreover, nearly all self-assembling systems reported to date use a single type of distinction. Developing systems where bi-or polyinstructional codes guide ...

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Section: Resultssupporting

confidence: 56%

Section: Resultsmentioning

confidence: 79%

Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Discrete and polymeric self-assembled dendrimers: Hydrogen bond-mediated assembly with high stability and high fidelity

Corbin

Lawless

et al. 2002

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

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170

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Molecular Recognition in Dendrimers

Basu

Sandanaraj

Thayumanavan

2004

Encyclopedia of Polymer Science and Technology

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Dendrimers are ideal candidates for molecular recognition applications, and this article addresses that theme. Synthetic approaches for achieving various dendrimers are discussed, because these methodologies form the basis for designing dendrimers for molecular recognition. Dendrimers act as host macromolecules, where the binding events occur due to a variety of attractive forces. This article focuses mainly on hydrogen‐bonding‐based recognition and hydrophobic forces. Recognition based on hydrogen bonding has been reported both within dendritic interiors and as a method to modify the surface functionalities of dendrimers. Both of these aspects are covered. The binding of guest molecules due to hydrophobic pressure, ie, amphiphilic dendrimers, is discussed.

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