Multivalence cooperativity leading to “all-or-nothing” assembly: the case of nucleation-growth in supramolecular polymers

Lopez-Fontal, Elkin; Milanesi, Lilia; Tomàs, Salvador

doi:10.1039/c6sc00520a

Cited by 12 publications

(19 citation statements)

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“…K o can be written as a function of the different binding constants for the formation of CB, C 2 B and CB 2 complexes. 31 The value of these binding constants is however the same, within the error, for different buffer concentrations (i.e., 5 and 100 mM) which means that K o does not depend on the concentration of buffer. 31 This result suggests that the bipyridine ligand keeps the anionic porphyrin rings far apart enough to render electrostatic repulsion between them negligible within the single stranded oligomers.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 88%

“…We have recently shown, 31 cobalt metalloporphyrin C and bipyridine B form complexes of the form CB, with a binding constant K 1 of 1.14x10 6 M -1…”

Section: Resultsmentioning

confidence: 99%

“…31 However, addition of salt to a sample of C and B both 10 M results in the growth of a red-shifted Soret band, characteristic of the formation of the double stranded polymer, when the concentration of salt approaches 100 mM (Figure 2A). Similarly, increasing the concentration of buffer in a sample containing equimolar C and B 25 M leads to the loss of the NMR signals assigned to C, consistent with the formation of large polymers ( Figure 2B).…”

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confidence: 99%

“…For simplicity of notation, we call the repeat units within the double-stranded polymer D, so that (M n ) 2 . C Molecular model of the double stranded polymer, derived from a crystal structure of the C and B complex 31,32 (top). In the bottom, the same model is shown in a CPK representation, with Na cations placed in the cavities defined by the sulfonate groups.…”

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confidence: 99%

“…C and B form linear oligomers by the alternating assembly of C and B building blocks. 31 These oligomers dimerize, leading to double stranded polymers. The formation of these polymers follows a nucleation-growth mechanism, which we have described using a model that combines the isodesmic oligomerization of single stranded oligomers (characterized by the oligomerization constant K o ) with the dimerization of the oligomers into double stranded polymers (characterized by the lateral association constant K l ).…”

Section: Introductionmentioning

confidence: 99%

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Modulation of the cooperativity in the assembly of multistranded supramolecular polymers

Campanella

Lopez-Fontal

Milanesi

et al. 2017

Phys. Chem. Chem. Phys.

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It is highly desirable that supramolecular polymers self-assemble following small changes in the environment. The degree of responsiveness depends on the degree of cooperativity at play during the assembly. Undertanding how to modulate and quantify cooperativity is therefore highly desirable for the study and design of responsive polymers. Here we show that the cooperative assembly of a porphyrin-based, double-stranded polymer is triggered by changes in building blocks and in salt concentration. We develop a model that accounts for this responsiveness by assuming the binding of the salt countercations to the double-stranded polymer. Using our assembly model we generate plots that show the increase in concentration of polymer versus the normalized concentration of monomer. These plots are ideally suited to appreciate changes in cooperativity, and show that, for our system, these changes are consistent with the increase in polymer length observed experimentally. Unexpectedly, we find that polymer stability increases when cooperativity decreases. We attribute this behaviour to the fact that increasing salt concentration stabilizes the overall polymer more than the nucleus. In other words, the cooperativity factor , defined as the ratio between the growth constant Kg and the nucleation constant Kn decreases as the overall stability of the polymer increases. Using our model to simulate the data, we generate cooperativity plots to explore changes in cooperativity for multistranded polymers. We find that, for the same pairwise association constants, the cooperativity sharply increases with the number of strands in the polymer. We attribute this dependence to the fact that the larger the number of strands, the larger is the nucleus necessary to trigger polymer growth. We show therefore that the cooperativty factor  does not properly account for the cooperativity behaviour of multistranded polymers, or any supramolecular polymer with a nucleus composed of more than 2 building blocks, and propose the use of the corrected cooperativity factor m. Finally, we show that multistranded polymers display highly cooperative polymerisation with pairwise association constants as low as 10 M -1 between the building blocks, which should simplify the design of responsive supramolecular polymers.

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confidence: 88%

“…We have recently shown, 31 cobalt metalloporphyrin C and bipyridine B form complexes of the form CB, with a binding constant K 1 of 1.14x10 6 M -1…”

Section: Resultsmentioning

confidence: 99%

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Modulation of the cooperativity in the assembly of multistranded supramolecular polymers

Campanella

Lopez-Fontal

Milanesi

et al. 2017

Phys. Chem. Chem. Phys.

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Analyzing Catalytic Co‐operativity and Membrane Parameters in a Substrate‐driven Vesicular Assembly Modified by Nucleotides

2022

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Rationalizing changes in functional properties by an exogenous module in a synthetic nanoscale self-organized system has broader significance in designing responsive biomimic materials having application in catalysis to therapeutics. Herein, we have developed a substrate-driven nanoscale vesicular assembly of a metallosurfactant (with dipicolylamine co-ordinated with zinc ion as headgroup) which simultaneously acts as a cooperative catalyst for the hydrolysis of the RNA-model substrate, 2-hydroxypropyl-4nitrophenylphosphate (HPNPP). We have found out that both purine and pyrimidine-based nucleoside monophosphates interact differently with the assembly, modulating the rate of catalytic cleavage. The different means of recognition of the nucleobases leads to alteration in membrane fluidity as well as surface charge of the vesicular aggregates whether the assembly is in catalytically active or inactive state. Then a systematic pattern for different nucleotides mediated vesicular nanoscale assembly composed of a catalytically-active surfactant by statistically corelating alteration in dynamic membrane parameters (fluidity, surface charge) with its cooperative phosphodiester hydrolyzing ability has been generated using principal component analysis as statistical tool. Overall, it showed a unique response pathway of a cooperative functional assembly to different exogenous modules, and this perception of the deconvolution of collective property opens up an avenue for future development of advanced adaptive systems.

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Multiplexed Profiling and Data Processing Methods to Identify Temperature-Regulated Primary Metabolites Using Gas Chromatography Coupled to Mass Spectrometry

Erban

Martinez‐Seidel

Rajarathinam

et al. 2020

Methods in Molecular Biology

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Multivalence cooperativity leading to “all-or-nothing” assembly: the case of nucleation-growth in supramolecular polymers

Abstract: All-or-nothing supramolecular polymerization: the role of multivalence cooperativity in multi-stranded polymers.

Cited by 12 publications

References 40 publications

Modulation of the cooperativity in the assembly of multistranded supramolecular polymers

Modulation of the cooperativity in the assembly of multistranded supramolecular polymers

Analyzing Catalytic Co‐operativity and Membrane Parameters in a Substrate‐driven Vesicular Assembly Modified by Nucleotides

Multiplexed Profiling and Data Processing Methods to Identify Temperature-Regulated Primary Metabolites Using Gas Chromatography Coupled to Mass Spectrometry

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