Supramolecular Polymer Chemistry:  Self-Assembling Dendrimers Using the DDA·AAD (GC-like) Hydrogen Bonding Motif

Ma, Yuguo; Kolotuchin, Sergei; Zimmerman, Steven C.

doi:10.1021/ja0202006

Cited by 180 publications

(86 citation statements)

References 25 publications

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“…[10][11][12] Although these non-covalent associations are usually weaker and reversible when compared to most covalent interactions, ionically driven attractions exhibiting multiple interactions per specie can result in very strong binding energies. [13,14] Incorporation of these interactions has also facilitated the construction of materials and devices for applications in photonics, [15] electronics, [16] conducting polymers, [17] and polyelectrolytes.[18]Herein, we report the ion-promoted, automorphogenic, [19] and stoichiometric self-assembly of nanoscale composite fibers using a structurally rigid hexameric macrocycle [( 1 12þ )(PF (1) 9 (3)] m . These polyanionic dense-packed counterions led to ion pair superstructures in which the randomness of singly-charged counterions was eliminated.…”

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confidence: 99%

Dendrimer–Metallomacrocycle Composites: Nanofiber Formation by Multi‐Ion Pairing

et al. 2008

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Non-covalent self-assembly via hydrogen bonding, van der Waals, and coordinative or ionic interactions [1] have found widespread application enroute to supramolecular assemblies. [2][3][4] Examples of ion-based materials include a molecular capsule [5] made by two oppositely charged calix [4] arenes, pseudorotaxanes [6] accessed by ion-pair templation, polyelectrolyte-amphiphile monolayers, [7][8][9] and ion-pair interactions between biomolecular recognition sites and their guests. [10][11][12] Although these non-covalent associations are usually weaker and reversible when compared to most covalent interactions, ionically driven attractions exhibiting multiple interactions per specie can result in very strong binding energies. [13,14] Incorporation of these interactions has also facilitated the construction of materials and devices for applications in photonics, [15] electronics, [16] conducting polymers, [17] and polyelectrolytes.[18]Herein, we report the ion-promoted, automorphogenic, [19] and stoichiometric self-assembly of nanoscale composite fibers using a structurally rigid hexameric macrocycle [( 1 12þ )(PF (1) 9 (3)] m . These polyanionic dense-packed counterions led to ion pair superstructures in which the randomness of singly-charged counterions was eliminated.Numerous examples of these Ru-based cyclized metallomers have been reported. [23][24][25][26][27][28][29][30] In this instance, meta-substituted bis(terpyridinyl)arene building blocks [31][32][33] constructed with either hydrocarbon aliphatic chains [34] or PEG-moieties [35] were incorporated to increase the solubility of these selfassembled metallohexamers in organic or aqueous solutions, respectively. This solubility enhancement resulted in the increase of the yields of the macrocyclization products. ) 12 ] (8.5 mg, 1.4 mM) and allowed to set undisturbed at 25 8C for two weeks (Fig. 1) in a sealed vial. After several hours, the formation of a cotton-like fiber was observed, and after 12 days, the solution became completely colorless, indicative of a self-assembly process. The resultant red fibers were filtered and washed sequentially with MeCN (3 Â 5 ml) then water (5 Â 5 ml) to remove traces of starting materials, if present, and any inorganic salts. In comparison, mixing 12 equiv. of NaOAc and 1 equiv. of [ (1 12þ )(PF

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confidence: 99%

Dendrimer–Metallomacrocycle Composites: Nanofiber Formation by Multi‐Ion Pairing

et al. 2008

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“…and for a full discussion the reader is directed to a number of excellent reviews In an attempt to provide this type of assembly with additional specificity and control, Zimmerman and co-workers have also developed supramolecular dendrimers which use a DDA . AAD hydrogen bonding motif (D: hydrogen-bond donor; A: hydrogen bond acceptor) to assemble individual dendrons into hexameric rosettes [6]. All studies were consistent with a cooperative aggregation process, and it was observed that decreasing the concentration, increasing the temperature or adding a competitive solvent shifted the equilibrium back from hexameric rosette towards monomer -clearly illustrating the reversibility of this type of assembly process.…”

Section: Introductionmentioning

confidence: 68%

Self-assembly using dendritic building blocks—towards controllable nanomaterials

Smith

Hirst

Love

et al. 2005

Progress in Polymer Science

175

100

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“…41,42 For example, Zimmerman and co-workers find that I-46 -G1 which contains DAA and DDA H-bonding faces with 60˚ relative orientation undergoes self-assembly to yield hexamer (I-46 -G1) 6 (Scheme I-11) as evidence by size exclusion chromatography (SEC). Similarly, dimeric compound I-47 -G3 with its self-complementary DDAA faces forms an exceptionally stable cyclic hexamer (I- 6 by H-bonding interactions.…”

Section: Zn(ii)mentioning

confidence: 99%

Complex Self‐Sorting Systems

Ghosh

2009

Dynamic Combinatorial Chemistry

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Over the past century scientists have taken a reductionist approach towards much of the physical and biological sciences. More recently scientists have become interested in constructing complex systems from their components and thereby controlling their emerging behaviors. As supramolcular chemists we have been pursuing an approach to the creation of complex functional systems -systems chemistry -by preparation of self-sorting systems. Self-sorting system displays ability to efficiently distinguish between self-and non-self even within complex mixture. This dissertation is divided into four chapters that describe increasingly complex self-sorting systems.Chapter 1 describes a literature review on self-sorting. First, we introduced the concept of self-sorting and then described the previously studied self-sorting phenomenon in the Isaacs group followed by a description of the examples of selfsorting systems in the literature.Chapter 2 describes the synthesis and characterization of eleven C-shaped methylene bridged glycoluril dimers (II-1 -II-11) bearing H-bonding groups on their aromatic rings. Compounds II-1, II-2, (±)-II-4a, (±)-II-5, and II-7 form tightly associated homodimers in CDCl 3 due to π -π and H-bonding interactions.Compounds II-2, (±)-II-5 and II-7, having disparate spatial distribution of their Hbonding groups show the ability to efficiently distinguish between self and non-self within three component mixtures in CDCl 3 . The effect of various structural modifications (e.g. chirality, side chain steric bulk, relative orientation, number and pattern of H-bonds) on the strength of self-assembly and the fidelity of self-sorting are presented.Chapter 3 describes the stepwise construction of an 8-component self-sorted system (III-1 -III-8) by the sequential addition of components. This process occurs via a large number of states (2 8 = 256) and even a larger number of pathways (8! = 40320). A pathway (III-5, III-6, III-7, III-8, III-4, III-3, III-2, then III-1) that is self-sorted at every step along the way. Another pathway (III-1, III-8, III-3, III-5, III-4, III-7, III-2, then III-6) exhibits interesting shuttling of guest molecules among hosts. The majority of pathways -unlike the special ones described above -proceed through several non self-sorted states. We characterized the remainder of the 40320 pathways by simulation using GEPASI and describe the influence of concentration, mean binding constants and standard deviation on the fidelity of the self-sorting pathways.Chapter 4 describes a method to control biological catalysis using synthetic self-sorting systems. We report the synthesis of IV-1 -IV-5 which contain both enzyme inhibitor and cucurbit[n]uril binding domains. The enzyme binding domains of IV-1 -IV-5 bind to the active sites of Bovine Carbonic Anhydrase or Acetylcholinesterase and inhibit their catalytic activities. Addition of CB [7] catalyzes the dissociation of IV-1 and IV-2 from the active site of BCA and thereby regenerates the enzymatic activity. In contrast, addition of CB [7] to...

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Supramolecular Polymer Chemistry: Self-Assembling Dendrimers Using the DDA·AAD (GC-like) Hydrogen Bonding Motif

Cited by 180 publications

References 25 publications

Dendrimer–Metallomacrocycle Composites: Nanofiber Formation by Multi‐Ion Pairing

Dendrimer–Metallomacrocycle Composites: Nanofiber Formation by Multi‐Ion Pairing

Self-assembly using dendritic building blocks—towards controllable nanomaterials

Complex Self‐Sorting Systems

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