Poly(methyl methacrylate)s with Pendant Calixpyrroles and Crown Ethers: Polymeric Extractants for Potassium Halides

Aydogan, Abdullah; Coady, Daniel J.; Kim, Sung Kuk; Akar, Ahmet; Bielawski, Christopher W.; Márquez, Manuel; Sessler, Jonathan L.

doi:10.1002/anie.200803970

Cited by 101 publications

(58 citation statements)

References 27 publications

(27 reference statements)

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“…16,17 For ion receptors for either cations or anions, their binding constants have been reported to vary significantly, especially in low dielectric constant media, depending on receptor concentration, ionic guest and its counterion concentrations, and nature of ions because interactions between receptors or/and between guests often make a remarkable influence on the formation of host/guest complexes. [18][19][20] However, this disadvantage can be somewhat overcome by decreasing the concentration of free counter ions as a result of complexing both cations and anions simultaneously using ditopic receptors or molecularly separated binary host systems. This is attributable to the fact that the bound ion pairs are protected better from the forced interaction with other free ion pairs which have been known to make an adverse effect on complexation between receptors and ions.…”

Section: List Ofmentioning

confidence: 99%

Calix[4]pyrrole-Based Ion Pair Receptors

2014

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Ion pair receptors, which are able to bind concurrently both a cation and an anion, often display higher selectivity and affinity for specific ion pairs than simple ion receptors capable of recognizing primarily either a cation or an anion. This enhancement in recognition function is attributable to direct or indirect cooperative interactions between cobound ions via electrostatic attractions between oppositely charged ions, as well as to positive allosteric effects. In addition, by virtue of binding the counterions of the targeted ion, ion pair receptors can minimize the solvation of the counterions, which can otherwise have a negative effect on the interactions between the receptors and the targeted ions. As a result of their more favorable interactions, ion pair receptors are attractive for use in applications, such as extraction and sensing, where control of the binding interactions is advantageous. In this Account, we illustrate this potential in the context of ion pair receptors based on the calix[4]pyrrole scaffold. Both simple ditopic ion pair receptors, containing sites for the recognition of a single anion and single cation, and so-called multitopic ion pair receptors will be discussed. The latter systems differ from conventional, so-called ditopic ion pair receptors in that they contain more than one binding site for a given targeted ion (e.g., a cation). This permits a level of selectivity and control over binding function not normally seen for simple ion or ion pair receptors containing one or two binding sites, respectively. Calix[4]pyrroles are macrocyclic compounds consisting of four pyrrole units linked via fully substituted sp 3 hybridized meso carbon atoms. They are effective receptors for Lewis basic anions (e.g., halides) in typical organic media and under certain conditions will recognize ion pairs containing charge diffuse cations, such as a small alkylammonium, imidazolium, or cesium cations. The calix[4]pyrrole framework is further attractive in that it is relatively easy to modify. In particular, functionalization of the β-pyrrolic carbon and meso-carbon atoms with simple crown ethers or calix[4]arene crown ethers can produce heteromultitopic ion pair receptors containing more than two cation binding sites. This allows the interactions between receptors and ions to be manipulated on a higher level than can be achieved using simple ion receptors or heteroditopic ion pair receptors and has made these systems attractive for use in ion transport, recognition, and extraction. Recent progress in developing calix[4]pyrroles as both multitopic and more conventional ion pair receptors is summarized in this Account. The emphasis will be on our own work.

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Section: List Ofmentioning

confidence: 99%

Calix[4]pyrrole-Based Ion Pair Receptors

2014

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“…Figure depicts the response of the CE Devices incorporating the three different crown ether materials as a function of time. Although 15C5 is reported to exhibit Na + binding in other nonelectronic sensor applications (Aydogan et al., ; Datta, ; Marsella & Swager, ; Nandhikonda et al., ), when these devices were exposed to NaCl analyte solutions, there was an increase in signal similar to that observed in the Reference Devices (Figure ). As such, it would appear that even with the 15C5 present as a binding layer, the addition of Na + still results in an increase in the conductivity of the P3HT layer.…”

Section: Resultsmentioning

confidence: 73%

“…In order to develop a sensor specific to the detection of Na + , a Na + -selective moiety which modulates the degree to which this ion-enhanced doping occurs must first be incorporated into the device. Here, crown ethers, which are known for their use in the extraction of metal cations from solutions (Aydogan et al, 2008), were selected for this purpose. The crown ether molecule size, and hence cavity dimension, affects the types of metal ions which can most easily interact with the binding site (Maleknia & Brodbelt, 1992).…”

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confidence: 99%

Organic electronics incorporating crown ethers as Na⁺ binding elements, towards a simple printable hydration sensor

et al. 2018

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Here, we present the development of organic electronic sensors containing crown ethers as ion binding elements for application in Na+ detection for health monitoring. The design, fabrication and characterization of chemiresistor‐based sensors using simple solution processing methods amenable to printing were demonstrated. The analyte testing comprised aqueous solutions of sodium chloride (0, 20, 50, 80 and 130 mM), with the Na+ concentration reflecting the range which occurs in human sweat. The introduction of the crown ether binding sites into the sensors was an iterative process, with three types of molecules trialled. The most effective molecule was found to be poly[(dibenzo‐18‐crown‐6)‐co‐formaldehyde], a polymer which comprises a linked chain of crown ether subunits. The binding of Na+ ions to the crown ether sites of the polymer was measured by comparing the amperometric characteristics of devices without crown ether binding sites (Reference Device) to those with crown ether binding sites (CE Device), following exposure to an analyte solution. For an 80 mM Na+ analyte solution, we observed a sensor response of 116.2 nA (It = 600 s) for the Reference Device (average) reduce to a value of 44.8 nA (It = 600 s) for the CE Device (average). This sensor shows a proof of concept towards low‐cost, solution‐processable sodium ion sensors suitable for mass production on flexible substrates.

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“…, K + and Na + ). In 2008, Sessler, Bielawski, and coworkers addressed this issue by appending benzo-[15]-crown-5-ether, a subunit known for its ability to complex cationic species [67], as a pendant group to the calix[4]pyrrole functionalized PMMA polymer backbone [68]. The resulting copolymer ( i.e.…”

Section: Polymers Containing Neutral Anion Receptorsmentioning

confidence: 99%

“…Ed. 2008 , 47 , 9648–9652 (Copyright Wiley-VCH GmbH & Co. KGaA), is reproduced with permission [68]. …”

Section: Figuresmentioning

confidence: 99%

Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

Rambo

Silver

Bielawski

et al. 2010

Topics in Heterocyclic Chemistry

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This chapter covers recent advances in the development of polymeric materials containing discrete heterocyclic anion receptors, and focuses on advances in anion binding and chemosensor chemistry. The development of polymers specific for anionic species is a relatively new and flourishing area of materials chemistry. The incorporation of heterocyclic receptors capable of complexing anions through non-covalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymer materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous environments. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions.

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Poly(methyl methacrylate)s with Pendant Calixpyrroles and Crown Ethers: Polymeric Extractants for Potassium Halides

Cited by 101 publications

References 27 publications

Calix[4]pyrrole-Based Ion Pair Receptors

Calix[4]pyrrole-Based Ion Pair Receptors

Organic electronics incorporating crown ethers as Na⁺ binding elements, towards a simple printable hydration sensor

Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

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Poly(methyl methacrylate)s with Pendant Calixpyrroles and Crown Ethers: Polymeric Extractants for Potassium Halides

Cited by 101 publications

References 27 publications

Calix[4]pyrrole-Based Ion Pair Receptors

Calix[4]pyrrole-Based Ion Pair Receptors

Organic electronics incorporating crown ethers as Na+ binding elements, towards a simple printable hydration sensor

Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

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Organic electronics incorporating crown ethers as Na⁺ binding elements, towards a simple printable hydration sensor