Supramolecular polymerization in water harnessing both hydrophobic effects and hydrogen bond formation

Leenders, Christianus M. A.; Albertazzi, Lorenzo; Mes, Tristan; Koenigs, Marcel M. E.; Palmans, Anja R. A.; Meijer, E. W.

doi:10.1039/c3cc38949a

Cited by 161 publications

(262 citation statements)

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“…1A). Neutral BTA monomers have been coassembled together with cationic species, indicated as BTA 3+ , into multicomponent one-dimensional structures (9). BTA 3+ are asymmetric monomers bearing at the PEG termini two primary amines, positively charged at neutral pH, and a cyanine dye (Cy3 or Cy5, both bearing one positive charge) as a fluorescent label.…”

Section: Resultsmentioning

confidence: 99%

“…The detailed procedures for the synthesis are reported in SI Text. The synthesis of neutral pegylated BTAs was previously reported (9). For BTA polymers assembly procedure stock solution of BTA (10 mM) and labeled BTA 3+ (1 mM) in MeOH were prepared.…”

Section: Methodsmentioning

confidence: 99%

“…Of particular relevance for the present work, is the fact that reversible interactions between monomers confer a dynamic behavior to BTA supramolecular polymers, wherein monomers are constantly being exchanged with the bulk (8). Most of these studies were in organic solvent, but we recently describe how pegylated BTAs self-assemble in water through a combination of hydrogen bonding and hydrophobic effects to create long supramolecular polymers of ∼0.1-10 μm in length (9).…”

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confidence: 99%

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Spatiotemporal control and superselectivity in supramolecular polymers using multivalency

Albertazzi

Martínez-Veracoechea

Leenders

et al. 2013

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

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117

171

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Multivalency has an important but poorly understood role in molecular self-organization. We present the noncovalent synthesis of a multicomponent supramolecular polymer in which chemically distinct monomers spontaneously coassemble into a dynamic, functional structure. We show that a multivalent recruiter is able to bind selectively to one subset of monomers (receptors) and trigger their clustering along the self-assembled polymer, behavior that mimics raft formation in cell membranes. This phenomenon is reversible and affords spatiotemporal control over the monomer distribution inside the supramolecular polymer by superselective binding of single-strand DNA to positively charged receptors. Our findings reveal the pivotal role of multivalency in enabling structural order and nonlinear recognition in watersoluble supramolecular polymers, and it offers a design principle for functional, structurally defined supramolecular architectures.self-assembly | simulations | energy transfer O ne of the most fascinating features of living matter is the precise control over biological activity in space and time.The cell membrane provides a remarkable example of such highfidelity spatiotemporal control in a complex biological setting, wherein thousands of different components, namely lipids and proteins, self-assemble into a 2D fluid mosaic (1). To perform the functions that the cell requires, lipids and proteins are heterogeneously distributed and specific biomolecules are segregated in active nanometer-sized domains often referred to as rafts (2). This distribution is highly dynamic, such that these platforms can be rapidly assembled and disassembled (3). The principles that underlie control over the molecular composition of the cellular microenvironment in space and time are the subject of great scientific debate as they are of crucial importance for cell functioning, signaling, growth, and division (4).One of the main goals of supramolecular chemistry is the noncovalent synthesis of functional molecular architectures through weak and reversible interactions (5). In this framework, a key challenge is the design of molecular building blocks that are able to self-organize hierarchically and in a cooperative fashion (6), thus mimicking the dynamic and structural complexity of living systems as well as their functionality. Various modular multicomponent systems have been successfully developed (7), but the spatiotemporal control of the localization of distinct components within synthetic supramolecular assemblies has yet to be realized. Mastering the spatial distribution of assembled molecules in a noncovalent synthesis is as crucial for their functionality as regio-selectivity impacts the molecular properties of organic molecules synthesized in a classical covalent manner. An interesting supramolecular polymer, where multiple components coassemble cooperatively in water, is based on 1,3,5-benzenetricarboxamide derivatives (BTAs) (8).Of particular relevance for the present work, is the fact that reversible interactions between ...

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Spatiotemporal control and superselectivity in supramolecular polymers using multivalency

Albertazzi

Martínez-Veracoechea

Leenders

et al. 2013

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

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117

171

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“…This tool has been widely used to probe the formation of hydrophobic pockets within self-assembled structures. [39][40][41] The addition of copolymers (P1-P5) resulted in a blue shift of 27 nm for the emission wavelength of Nile Red in water. The fluorescence intensity also increased significantly in the presence of the polymers (Fig.…”

Section: CD Dls and Fluorescence Characterization Of P1-p5 In Solutionmentioning

confidence: 99%

Understanding the catalytic activity of single‐chain polymeric nanoparticles in water

Artar

Terashima

Sawamoto

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

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ABSTRACT:The structuring role of benzene-1,3,5-tricarboxamide (BTA) groups for the catalytic activity of single chain polymeric nanoparticles in water was investigated in the transfer hydrogenation of ketones. To this end, a set of segmented, amphiphilic copolymers was prepared, which comprised oligo (ethylene glycol) side chains to impart water solubility, BTA and/or lauryl side chains to induce hydrophobicity and diphenylphosphinostyrene (SDP) units in the middle part as a ligand to bind a ruthenium catalyst. All copolymers were obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization and showed low dispersities (M w /M n 5 1.23-1.38) and controlled molecular weights (M n 5 44-28 kDa). A combination of circular dichroism (CD) spectroscopy and dynamic light scattering (DLS) showed that all copolymers fold into a single chain polymeric nanoparticles (SCPNs) as a result of the helical selfassembly of the pendant BTA units and/or hydrophilic-hydrophobic phase separation. To create catalytic sites, RuCl 2 (PPh 3 ) 3 was incorporated into the copolymers. The Cotton effects of the copolymers before and after Ru(II) loading were identical, indicating that the helical self-assembly of the BTA units and the complexation of SDP ligands and Ru(II) occurs in an orthogonal manner. DLS revealed that after Ru(II) loading, SDP-bearing copolymers retained their single chain character in water, while copolymers lacking SDP units clustered into larger aggregates. The Ru(II) loaded SCPNs were tested in the transfer hydrogenation of cyclohexanone. This study reveals that BTA induced stack formation is not crucial for SCPN formation and catalytic activity; SDP-bearing copolymers folded by Ru(II) complexation and hydrophobic pendants suffice to provide hydrophobic, isolated reaction pockets around Ru(II) complexes. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52,[12][13][14][15][16][17][18][19][20]

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“…Scheme 1 Synthetic route to 3a-c, Reaction of 1 (2.5 mm) with 2a-c (5 mm) and Et 3 N (5 mm) in THF (50 mL) at RT forces that put the building blocks (self-assemblies) into a well-defined nanoarchitecture can be understood and elaborated by many workers [40][41][42][43][44][45][46][47][48][49][50]. The organization of building blocks into ordered structures is facilitated by a combination of many different non-covalent interactions such as H-bonding, Pi-Pi stacking and hydrophobic interactions.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of nanoarchitectures from fatty acid derivatives of 2,6-diaminopyridine and 2-aminopyridine

Hassan

Rauf

2014

J Nanostruct Chem

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The self-assembling property of lipids makes it an important building block in the field of supramolecular nanoarchitectures with a variety of applications in chemistry, biochemistry, materials science and medicine. We report here, the synthesis and formation of variety of nanostructures such as nanosheets, nanofibers and nanotubes of fatty acid derivatives of 2,6-diaminopyridine and 2-aminopyridine. These molecules possess a saturated or unsaturated long alkyl-chain group as the self-assembling unit. The molecular recognition property of diaminopyridine linker as a result of H-bonding was confirmed by 1 H-NMR and fluorescence spectroscopy and it plays an important role in monitoring the chemical selectivity of supramolecular aggregates toward guest binding. The chemical structures were characterized by Fourier transform-infrared, 1 H-NMR, 13 C-NMR, mass spectra, whereas the morphologies were imaged using scanning electron microscopy and transmission electron microscopy.

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Supramolecular polymerization in water harnessing both hydrophobic effects and hydrogen bond formation

Cited by 161 publications

References 28 publications

Spatiotemporal control and superselectivity in supramolecular polymers using multivalency

Spatiotemporal control and superselectivity in supramolecular polymers using multivalency

Understanding the catalytic activity of single‐chain polymeric nanoparticles in water

Synthesis and characterization of nanoarchitectures from fatty acid derivatives of 2,6-diaminopyridine and 2-aminopyridine

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