Counterion Distribution around Hydrophilic Molecular Macroanions: The Source of the Attractive Force in Self‐Assembly

Pigga, Joseph M.; Kistler, Melissa L.; Shew, Chwen‐Yang; Antonio, Mark R.; Liu, Tianbo

doi:10.1002/ange.200902050

Cited by 32 publications

(23 citation statements)

References 53 publications

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“…A simple mean‐field model was developed to qualitatively elucidate the role of bound counterions in the attraction between two like‐charge macroanions, as well as the effect of the dielectric constant of the medium on the interplay between counterion binding and the self‐assembly of the like‐charge macroions. The results from experiment and calculation confirmed that macroion–counterion association is the pivotal contributing source of the attractive forces between the macroanions and, in turn, of their self‐assembly into blackberry structures in solution 32…”

Section: A Retrospective Summary On the Interaction Between Poms Amentioning

confidence: 68%

“…Macroanion–counterion interaction plays an important role in blackberry formation. In order to accurately describe the counterion association around macroions and to clarify its relation to the self‐assembly of hydrophilic macroions, SAXS was used to monitor the counterion distribution around 2.5 nm, hollow, spherical POM {Mo 72 V 30 } in water and mixed solvents (acetone/water) 32…”

Section: A Retrospective Summary On the Interaction Between Poms Amentioning

confidence: 99%

“…In very dilute solution of {Mo 72 V 30 }, each macroanion is assumed to carry 31 negative charges, with the counterions being 14 K + , 8 Na + , 2 VO 2+ , and 5 H + 32. The SAXS curve from the solution containing individual {Mo 72 V 30 } could be fit by the form factor of {Mo 72 V 30 } cluster.…”

Section: A Retrospective Summary On the Interaction Between Poms Amentioning

confidence: 99%

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Counterion Interaction and Association in Metal‐Oxide Cluster Macroanionic Solutions and the Consequent Self‐Assembly

Yin

Liu

2011

Israel Journal of Chemistry

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The interaction between large metal-oxide polyanions and their counterions is unique. Owing to their size disparity, there is a moderate ion-pairing effect and loose distribution of counterions around macroions, which leads to the unique solution behavior and the self-assembly of the macroions in polar solvents, and the counterion exchange capability around macroions. Furthermore, the macroioncounterion interaction also affects the catalytic behavior of the polyoxometalate (POM) clusters. Replacement of func-tionalized cations helps to modify the POM anions through static charge attraction. At the same time, the strong POMcounterion interaction can also lead to counterion-dependent synthesis. Recent developments on theoretical simulations help to understand this interaction at the molecular scale. This review summarizes the chronological progress of the exploration of macroion-counterion interaction (both theoretically and experimentally) and its impact on related research fields.

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Section: A Retrospective Summary On the Interaction Between Poms Amentioning

confidence: 68%

Section: A Retrospective Summary On the Interaction Between Poms Amentioning

confidence: 99%

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Counterion Interaction and Association in Metal‐Oxide Cluster Macroanionic Solutions and the Consequent Self‐Assembly

Yin

Liu

2011

Israel Journal of Chemistry

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“…These results all indicate that the counterions play an important role in this self‐assembly process, in analogy with the self‐assembly of POM macroanions 10. 15 The effective surface charge density of the macroanions is significantly lowered as a result of counterion association, which in turn reduces the repulsion force between two macroanions. In the solution of cationic M 12 L 24 , we believe that the counterion‐mediated attraction is the major driving force for self‐assembly 14.…”

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confidence: 86%

Viral‐Capsid‐Type Vesicle‐Like Structures Assembled from M₁₂L₂₄ Metal–Organic Hybrid Nanocages

et al. 2011

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Viral capsids contain multiple copies of identical monomer or dimer proteins arranged into monolayered spherical structures with icosahedral symmetry. These spherical structures (capsids) can wrap up the genome. For example, the capsids of wild hepatitis B virus (HBV) have a diameter of approximately 20 nm and contain 120 copies of a dimer protein. [1] The viral capsid proteins can also assemble into vesicles in vitro under appropriate conditions (e.g. high ionic strength, low pH value) without the viral genome. The hydrophobic interactions, hydrogen bonding, and electrostatic interactions between capsid monomers/dimers are important for the process. [1,2] For a better understanding of the complex nature of viral-capsid formation, and the breathing and swelling modes of the virus, simple analogous model systems are needed to mimic the self-assembly process of viral capsids. [3] Although hydrophobic interactions are generally believed to be the major driving force for the construction of viral capsids, they cannot explain some phenomena, such as the salt effect. [1,4] On the other hand, underestimated electrostatic interactions might play a role, as the proteins are charged macroions. One important factor which may reflect the nature of attractive interactions is the interparticle distance between the building blocks on the surface of the assembled structures. However, this crucial information is usually difficult to obtain.Recent studies have shown that hydrophilic macroions with sizes between those of simple ions and large colloids behave completely differently from smaller and larger macroions. Both macroanions (including various polyoxometalates, or POMs) and macrocations (such as metal-organic nanocages) slowly assemble into single-layered, spherical, vesiclelike "blackberry" structures in polar solvents. [5] However, a major difference between metal-organic nanocages and POMs is that the former entities contain multiple hydrophobic domains, which might affect the self-assembly process by introducing additional driving forces. This postulate has not yet been confirmed. This special feature makes inorganicorganic nanocages more complex systems than POMs, but also more interesting, as many biological assembly processes also involve hydrophobic interactions and electrostatic interactions. [6] Herein, we focus on the study of organic-inorganic nanocages of the type M 12 L 24 (M = Pd, L = 2,6-bis(4-pyridylethynyl)toluene) in solution. They are novel macromolecules assembled from small building blocks of organic ligands and metal ions. Their shape, size, charge, and composition can be rationally designed by judicious selection of the metal ions and the organic ligands. [7] Such nanocages exist as macrocations in solution and are soluble in polar solvents owing to the charges at the metal centers. The thermodynamic stability, encapsulation, and catalytic properties of M 12 L 24 nanocages have been studied in detail. [8] Unlike the M 6 L 4 nanocages that we studied previously, which have an octahedral geometry with...

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“…[4c] In particular, counterion distribution around hydrophilic macroanions and selective monovalent cation association and exchange around Keplerate POM macroanions in dilute aqueous solutions are unique and directly related to their self-assembly process. [19] On the other hand, counterions can also affect the behavior of common surfactants in aqueous solution at air/solution interfaces or at solid/solution interfaces and in the micelle-to-vesicle transition processes. [20] Therefore, the effect of counterions on the self-assembly of POM-containing hybrids is an interesting avenue, worth further investigation.…”

Section: Effect Of Counterionsmentioning

confidence: 99%

Controllable Self‐Assembly of Organic–Inorganic Amphiphiles Containing Dawson Polyoxometalate Clusters

Yin

Pradeep

Zhang

et al. 2012

Chemistry A European J

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An organic-inorganic molecular hybrid containing the Dawson polyoxometalate, ((C(4)H(9))(4)N)(5)H[P(2)V(3)W(15)O(59)(OCH(2))(3)CNHCOC(15)H(31)], was synthesized and its surfactant-like amphiphilic properties, represented by the formation of bilayer vesicles, were studied in polar solvents. The vesicle size decreases with both decreasing hybrid concentration and with increasing polarity of the solvent, independently. The self-assembly behavior of this hybrid can be controlled by introducing different counterions into the acetonitrile solutions. The addition of ZnCl(2) and NaI can cause a gradual decrease and increase of vesicular sizes, respectively. Tetraalkylammonium bromide is found to disassemble the vesicle assemblies. Moreover, the original counterions of the hybrid can be replaced with protons, resulting in pH-dependent formation of vesicles in aqueous solutions. The hybrid surfactant can further form micro-needle structures in aqueous solutions upon addition of Ca(2+) ions.

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Counterion Distribution around Hydrophilic Molecular Macroanions: The Source of the Attractive Force in Self‐Assembly

Cited by 32 publications

References 53 publications

Counterion Interaction and Association in Metal‐Oxide Cluster Macroanionic Solutions and the Consequent Self‐Assembly

Counterion Interaction and Association in Metal‐Oxide Cluster Macroanionic Solutions and the Consequent Self‐Assembly

Viral‐Capsid‐Type Vesicle‐Like Structures Assembled from M₁₂L₂₄ Metal–Organic Hybrid Nanocages

Controllable Self‐Assembly of Organic–Inorganic Amphiphiles Containing Dawson Polyoxometalate Clusters

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Counterion Distribution around Hydrophilic Molecular Macroanions: The Source of the Attractive Force in Self‐Assembly

Cited by 32 publications

References 53 publications

Counterion Interaction and Association in Metal‐Oxide Cluster Macroanionic Solutions and the Consequent Self‐Assembly

Counterion Interaction and Association in Metal‐Oxide Cluster Macroanionic Solutions and the Consequent Self‐Assembly

Viral‐Capsid‐Type Vesicle‐Like Structures Assembled from M12L24 Metal–Organic Hybrid Nanocages

Controllable Self‐Assembly of Organic–Inorganic Amphiphiles Containing Dawson Polyoxometalate Clusters

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Viral‐Capsid‐Type Vesicle‐Like Structures Assembled from M₁₂L₂₄ Metal–Organic Hybrid Nanocages