Nucleation–elongation: a mechanism for cooperative supramolecular polymerization

Zhao, Dahui; Moore, Jeffrey S.

doi:10.1039/b308788c

Cited by 433 publications

(469 citation statements)

References 76 publications

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“…Taking into account that, as shown above, the law of mass action is tightly linked to the way the grand partition function Z is defined, the application of the binding polynomial Z b to a particular system with cooperativity must be treated with caution. The cooperative self-and heteroassemblies have attracted a great deal of attention in supramolecular chemistry (see, e.g., [10,18,19]); this issue will not be discussed in the present paper. We must note, however, a specific partial case of cooperativity, reviewed in [20], which is fully compliant with the oligomer partition function (6) and hence with the binding polynomial Z b .…”

Section: Summary and Discussion Of Basic Assumptions Behind The Comentioning

confidence: 95%

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Binding polynomial in molecular self-assembly

et al. 2014

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In the present work the concept of a binding polynomial is revisited for the most widely used case of self-assembly of identical molecular units and results in the re-construction of a link to the grand partition function of such a system. It is found that if the self-assembly process is not pronounced (i.e., the product of the equilibrium constant and the monomer concentration is close to zero), the binding polynomial has the meaning of a molecular partition function that is given by the summation over energy levels of any molecule in the system. In other cases the concept of a binding polynomial may be misleading.

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Section: Summary and Discussion Of Basic Assumptions Behind The Comentioning

confidence: 95%

“…(f) Only a single way of formation of any i-mer X i is considered, viz., by sequential addition of a monomer X 1 to an (i -1)-mer X i −1 , commonly written in the form of an [1,3,18,19]. An alternative way, often called the random association X i + X j K ↔ X i+j reviewed in [3], is ignored.…”

Section: Summary and Discussion Of Basic Assumptions Behind The Comentioning

confidence: 99%

Binding polynomial in molecular self-assembly

et al. 2014

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“…15,16 In the isodesmic process, all growing steps are characterized by the same value of association constant regardless of the sizes of the aggregates. On the contrary, the cooperative mechanism is composed of two separate steps, in which a thermodynamically unfavorable initial nucleation is followed by a highly favored cooperative elongation process characterized by much higher binding constants.…”

Section: -7mentioning

confidence: 99%

“…Usually one assumes small seeds (n ≈ 2) in such models, but larger ones can also be adopted. 15 Since endergonic growths…”

Section: Aggregation Mechanisms and Cooperativitymentioning

confidence: 99%

Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition‐Metal Compounds: A Theoretical Study

Caturello

Csók

Fernández

et al. 2016

Chemistry A European J

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Abstract:The nature of intermolecular interactions governing supramolecular polymerizations is very important to control their cooperativity. In order to address this problem, supramolecular columns made of Pt(II) and Pd(II) complexes of oligo(phenylene ethynylene)-based pyridine (OPE) and tetrazolyl-pyridine ligands (TEP) were investigated through the dispersion-corrected PM6 method. Aromatic, CH-π, M-Cl and metallophilic interactions helped stabilize the supramolecules studied, and their geometries and associated cooperativities were in excellent agreement with experimental data. The OPE ligand and/or the presence of Pt(II) have led to stronger metallophilic interactions and also to cooperative supramolecular polymerizations, which clearly suggests that metallophilic interactions are a key factor to control cooperativity. The results indicate that sequential monomer addition is in general less spontaneous than the combination of two larger pre-formed stacks. The present theoretical investigations contribute to the further understanding of the relation between the thermodynamics of supramolecular polymerizations and the nature of different synthons.

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“…[13] Low molecular weight organic gelators (LMWG) offer an alternative synthetic route to obtain highly controlled fibrillar architectures. [14] Microfluidic flow reactors can be potentially employed to control the pH medium at the nanoscale by controlling the flow of different pH solutions and different concentrations of the LMWG solution. Microfluidic platforms allowing mixing have been proved to be excellent tools to study protein denaturation, [15] protein fibrillation, [16] RNA refolding.…”

Section: Introductionmentioning

confidence: 99%

Microfluidic Assisted Self‐Assembly of pH‐Sensitive Low‐Molecular Weight Hydrogelators Close to the Minimum Gelation Concentration

Hermida‐Merino¹,

Trebbin²,

Foerster

et al. 2015

Macromolecular Symposia

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Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication Citation for published version (APA):Hermida-Merino, D., Trebbin, M., Foerster, S., Rodriguez-Llansola, F., & Portale, G. (2015). Microfluidic assisted self-assembly of pH-sensitive low-molecular weight hydrogelators close to the minimum gelation concentration. Macromolecular Symposia, 358(1), 59-66. DOI: 10.1002/masy.201500032 General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Summary: The fibrillation and subsequent gelation of low molecular hydrogelators is usually triggered by external stimuli. Generally, strong acids are employed to trigger the self-assembly mechanism in pH-responsive supramolecular systems. However, the generation and design of novel stable gels with performing mechanical properties is a challenging task as a result of the uneven self-assembled networks formed. Here, we report the study of the self-assembly process of a low molecular weight hydrogelator (LMWG) in the proximity of its minimum gelation concentration (MGC ¼ 0.3 mg/ml). At such high dilution, the generation of homogeneous gels with good mechanical properties by turning pH by strong acids is a demanding task as a result of the lack of monodisperse 1D self-assembled rod-like aggregates. A microfluidic device is employed here to gradually and homogeneously change the pH. We show that self-assembly of LMWG in welldefined structures can be enhanced by using the diffusive mixing occurring in the microfluidic reactor channel. For very short mixing times, aggregates with 2 nm cross-section are found in the region adjacent to the focused LMWG solution ...

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Nucleation–elongation: a mechanism for cooperative supramolecular polymerization

Cited by 433 publications

References 76 publications

Binding polynomial in molecular self-assembly

Binding polynomial in molecular self-assembly

Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition‐Metal Compounds: A Theoretical Study

Microfluidic Assisted Self‐Assembly of pH‐Sensitive Low‐Molecular Weight Hydrogelators Close to the Minimum Gelation Concentration

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