Self‐Assembly Principles of Helicates

Hamacek, Josef

doi:10.1002/9781118517413.ch3

Cited by 12 publications

(10 citation statements)

References 71 publications

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“…The thermodynamics of multivalent supramolecular assembly can be summarized in terms of two main trends: the "principle of maximum occupancy," which refers to the tendency of systems to evolve toward the most stable state with full occupancy of binding sites, and the "entropy factor," which favors the state of the system with the largest number of product species (41). For most of the supramolecular systems studied to date, the valency (number of binding sites per monomer) is relatively small (<6), the principle of maximum occupancy dominates, and all sites are generally filled in the assembled materials (42,43). However, for high-valence monomers, such as the polyA chains studied here, the entropy factor strongly opposes the principle of maximum occupancy and more complex behavior emerges.…”

Section: Master Equations For High-valence Assemblymentioning

confidence: 87%

“…High-valence supramolecular systems have many useful properties that are only just beginning to be explored, such as the ability to self-heal, responsiveness to stimuli, and simple, inexpensive chemical derivatization. Examples include small molecule-directed nucleic acid assembly [CA + polyadenosine or polyA (17,29); melamine + polythymine (46)] and noncovalent polymer cross-linking via multiple metal chelation (42,47) or host/guest interactions (48,49).…”

Section: Master Equations For High-valence Assemblymentioning

confidence: 99%

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Using transient equilibria (TREQ) to measure the thermodynamics of slowly assembling supramolecular systems

et al. 2022

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Supramolecular chemistry involves the noncovalent assembly of monomers into materials with unique properties and wide-ranging applications. Thermal analysis is a key analytical tool in this field, as it provides quantitative thermodynamic information on both the structural stability and nature of the underlying molecular interactions. However, there exist many supramolecular systems whose kinetics are so slow that the thermodynamic methods currently applied are unreliable or fail completely. We have developed a simple and rapid spectroscopic method for extracting accurate thermodynamic parameters from these systems. It is based on repeatedly raising and lowering the temperature during assembly and identifying the points of transient equilibrium as they are passed on the up- and down-scans. In a proof-of-principle application to the coassembly of polydeoxyadenosine (polyA) containing 15 adenosines and cyanuric acid (CA), we found that roughly 30% of the CA binding sites on the polyA chains were unoccupied, with implications for high-valence systems.

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Section: Master Equations For High-valence Assemblymentioning

confidence: 87%

Section: Master Equations For High-valence Assemblymentioning

confidence: 99%

Using transient equilibria (TREQ) to measure the thermodynamics of slowly assembling supramolecular systems

et al. 2022

View full text Add to dashboard Cite

show abstract

“…High valence supramolecular systems have many useful properties that are only just beginning to be explored, such as the ability to self-heal, responsiveness to stimuli, and simple, inexpensive chemical derivatization. Examples include small molecule-directed nucleic acid assembly (CA + polyadenosine or polydeoxyadeonsine 14,17 ; melamine + polythymine 29 ) and non-covalent polymer crosslinking via multiple metal chelation 25,30 or host/guest interactions 31,32 . Equation 9 and Equation 10 can serve as starting points for quantitatively describing assembly in such systems, where simple probabilistic considerations ensure that some of the binding sites will remain vacant under many conditions.…”

Section: Master Equations For High-valence Assemblymentioning

confidence: 99%

Transient equilibrium mapping: A new tool for measuring the thermodynamics of slowly assembling supramolecular systems

Hennecker

Lachance‐Brais

Sleiman

et al. 2021

Preprint

View full text Add to dashboard Cite

Supramolecular chemistry involves the non-covalent assembly of monomers into materials with unique properties and wide-ranging applications. Thermal analysis is one of the key analytical tools in this field, as it provides quantitative thermodynamic information on both the structural stability and nature of the underlying molecular interactions. However there exist many supramolecular systems whose kinetics are so slow under conditions approaching chemical equilibrium that thermodynamic data are inaccessible. We have developed a simple, general, and rapid spectroscopic method for extracting thermodynamic parameters from such slowly assembling systems. It is based on repeatedly raising and lowering the temperature during assembly and identifying the points of transient equilibrium as they are passed on the up-and down-scans. In a proof-of-principle application to the slow co-assembly of polydeoxyadenosine containing 15 adenosines (polyA15) and cyanuric acid (CA), we found that roughly 30% of the CA binding sites on the polyA chains were unoccupied, with implications for the assembly of high-valence systems.

show abstract

“…High valence supramolecular systems have many useful properties that are only just beginning to be explored, such as the ability to self-heal, responsiveness to stimuli, and simple, inexpensive chemical derivatization. Examples include small molecule-directed nucleic acid assembly (CA + polyadenosine or polydeoxyadeonsine 14,17 ; melamine + polythymine 29 ) and non-covalent polymer crosslinking via multiple metal chelation 25,30 or host/guest interactions 31,32 . Equation 9and Equation 10 can serve as starting points for quantitatively describing assembly in such systems, where simple probabilistic considerations ensure that some of the binding sites will remain vacant under many conditions.…”

Section: Master Equations For High-valence Assemblymentioning

confidence: 99%

Transient equilibrium mapping: A new tool for measuring the thermodynamics of slowly assembling supramolecular systems

Hennecker

Lachance‐Brais

Sleiman

et al. 2021

Preprint

View full text Add to dashboard Cite

Supramolecular chemistry involves the non-covalent assembly of monomers into materials with unique properties and wide-ranging applications. Thermal analysis is a key analytical tool in this field, as it provides quantitative thermodynamic information on both the structural stability and nature of the underlying molecular interactions. However there exist many supramolecular systems whose kinetics are so slow under conditions approaching equilibrium that thermodynamic data are inaccessible. We have developed a simple and rapid spectroscopic method for extracting thermodynamic parameters from these systems. It is based on repeatedly raising and lowering the temperature during assembly and identifying the points of transient equilibrium as they are passed on the up- and down-scans. In a proof-of-principle application to the co-assembly of polydeoxyadenosine containing 15 adenosines (polyA15) and cyanuric acid (CA), we found that roughly 30% of the CA binding sites on the polyA chains were unoccupied, with implications for the assembly of high-valence systems.

show abstract

Self‐Assembly Principles of Helicates

Cited by 12 publications

References 71 publications

Using transient equilibria (TREQ) to measure the thermodynamics of slowly assembling supramolecular systems

Using transient equilibria (TREQ) to measure the thermodynamics of slowly assembling supramolecular systems

Transient equilibrium mapping: A new tool for measuring the thermodynamics of slowly assembling supramolecular systems

Transient equilibrium mapping: A new tool for measuring the thermodynamics of slowly assembling supramolecular systems

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