Tetra-TTF Calix[4]pyrrole:  A Rationally Designed Receptor for Electron-Deficient Neutral Guests

Nielsen, Kent A.; Cho, Won Seob; Jeppesen, Jan O.; Lynch, Vincent M.; Becher, Jan; Sessler, Jonathan L.

doi:10.1021/ja044664a

Cited by 159 publications

(81 citation statements)

References 9 publications

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“…level, confirming previous reports 13,21 ). Importantly, these devices demonstrate the need for electron-donating functional groups, for example, amine, thiol groups 9,39 and possibly calyx [4]pyrrole receptors 40 , required for the binding interaction of the electron-deficient explosive species to the nanosensors surface, and thus will be applied as the internal control sensors throughout our studies.…”

Section: Article Nature Communications | Doi: 101038/ncomms5195mentioning

confidence: 99%

Supersensitive fingerprinting of explosives by chemically modified nanosensors arrays

Lichtenstein¹,

Havivi²,

Shacham³

et al. 2014

Nat Commun

173

127

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The capability to detect traces of explosives sensitively, selectively and rapidly could be of great benefit for applications relating to civilian national security and military needs. Here, we show that, when chemically modified in a multiplexed mode, nanoelectrical devices arrays enable the supersensitive discriminative detection of explosive species. The fingerprinting of explosives is achieved by pattern recognizing the inherent kinetics, and thermodynamics, of interaction between the chemically modified nanosensors array and the molecular analytes under test. This platform allows for the rapid detection of explosives, from air collected samples, down to the parts-per-quadrillion concentration range, and represents the first nanotechnology-inspired demonstration on the selective supersensitive detection of explosives, including the nitro-and peroxide-derivatives, on a single electronic platform. Furthermore, the ultrahigh sensitivity displayed by our platform may allow the remote detection of various explosives, a task unachieved by existing detection technologies.

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Section: Article Nature Communications | Doi: 101038/ncomms5195mentioning

confidence: 99%

Supersensitive fingerprinting of explosives by chemically modified nanosensors arrays

Lichtenstein¹,

Havivi²,

Shacham³

et al. 2014

Nat Commun

173

127

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“…TTF-C4Ps, like other calix [4]pyrroles, can adopt several conformations, including the limiting cone and 1,3-alternate forms. In previous work, we found that these macrocycles would bind planar, electron-deficient nitroaromatics, including TNB, with a 1∶2 stoichiometry in their 1,3-alternate forms in the absence of anions (24,25). In contrast, the corresponding anion-stabilized cone forms would interact with larger electron-deficient species, as evidenced by the anion-triggered binding of C 60 (26) or the stabilization of a long-lived electron transfer state as the result of supramolecular capsule formation (27).…”

mentioning

confidence: 97%

Chemoresponsive alternating supramolecular copolymers created from heterocomplementary calix[4]pyrroles

Park

Yoon

Kim

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix [4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix [4] pyrrole. The resulting polymeric materials, stabilized by combination of donor-acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1-and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of "smart" sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling.cooperativity | sensing | supramolecular chemistry | supramolecular polymers | dynamic materials I n recent years, considerable effort has been devoted to the development of artificial supramolecular polymeric materials (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20). Much of the interest in these kinds of systems stems from an appreciation that they act as rudimentary models for some of the most fundamental, yet complex systems, found in nature. Living systems typically exploit multiple noncovalent interactions to drive the formation and stabilization of a wide variety of complex polymeric architectures for the implementation of function, codifying diversity, and imparting complexity. Because of their stabilization, in part by multiple weak forces, including hydrogen bonds, metal-ligand interactions, and donor-acceptor interactions, many of these architectures undergo considerable modification in their structure and function upon application of some external stress or exposure to a specific chemical trigger, as ill...

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“…Inspired by the biological ET systems mentioned above, we attempted to achieve control over ET within synthetic supramolecular ensembles through the judicious addition of anions and cations. As detailed below, we found that by using a mixture of the electron donating tetrathiafulvalene-appended calix [4]pyrrole (TTF-C4P) 21 with the dicationic electron acceptor bisimidazolium quinone (BIQ 2+ ) 22 we could reversibly switch the direction of electron transfer by varying the surrounding ionic environment. 23 Calix [4]pyrroles (C4P), in general, are a class of fluxional tetrapyrrolic macrocycles that bind selected anionic guests in organic solvents.…”

Section: Biological Systemsmentioning

confidence: 99%

Supramolecular electron transfer-based switching involving pyrrolic macrocycles. A new approach to sensor development?

et al. 2015

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This Feature focuses on pyrrolic macrocycles that can serve as switches via energy-or electron transfer (ET) mechanisms. Macrocycles operating by both ground state (thermodynamic) and photoinduced ET pathways are reviewed and their ability to serve as the readout motif for molecular sensors is discussed.The aim of this article is to highlight the potential utility of ET in the design of systems that perform molecular switching or logic functions and their applicability in chemical sensor development. The conceptual benefits of this paradigm are illustrated with examples drawn mostly from the authors' laboratories.

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Tetra-TTF Calix[4]pyrrole: A Rationally Designed Receptor for Electron-Deficient Neutral Guests

Cited by 159 publications

References 9 publications

Supersensitive fingerprinting of explosives by chemically modified nanosensors arrays

Supersensitive fingerprinting of explosives by chemically modified nanosensors arrays

Chemoresponsive alternating supramolecular copolymers created from heterocomplementary calix[4]pyrroles

Supramolecular electron transfer-based switching involving pyrrolic macrocycles. A new approach to sensor development?

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