Molecular Tweezers and Clips as Synthetic Receptors. Molecular Recognition and Dynamics in Receptor−Substrate Complexes

Klärner, Frank‐Gerrit; Kahlert, Björn

doi:10.1021/ar0200448

Cited by 369 publications

(244 citation statements)

References 36 publications

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“…Das elektronenreiche TTF-calix[4]pyrrol ist auch ein geeigneter Rezeptor für Fullerene und für elektronenarme neutrale Gastmoleküle. [235] Die Innenseite von konkav geformten aromatischen Cleft-oder Pinzettenverbindungen ist durch eine im Vergleich zur konvexen Außenseite stark erhöhte negative Partialladung gekennzeichnet, [236] wodurch elektronendefiziente Systeme effektiv komplexiert werden können (Schema 9). Die Stabilität der Komplexe in Chloroform nimmt mit dem Elektronendefizit der Gastmoleküle zu, dominiert durch Enthalpiegewinne und wenig beeinflusst durch entropische Beiträge.…”

Section: Elektrostatische Wechselwirkungenunclassified

“…Komplexe von elektronenreichen Cleft-oder Pinzettenverbindungen mit elektronenarmen Gastmolekülen; Aktivierungsenergien des Austauschs DG* in CDCl 3 . [236] H.-J. Schneider Aufsätze…”

Section: Elektrostatische Wechselwirkungenunclassified

“…[524] In Einklang mit einem überwiegend dispersiven Bindungsmechanismus nimmt die Affinität von C 60 -Fullerenen zu substituierten Calix[5]arenen mit zunehmender Polarisierbarkeit sowohl von Substituenten wie des Solvens zu (Schema S20). [525] Corannulene weisen eine konkave Struktur auf, die sich Fullerenen gut anpasst (Schema S21); zudem besitzen sie ähnlich wie Tweezer-Gastverbindungen [236] an der konkaven Oberfläche eine negative Partialladung. Daher werden mit den elektronendefizienten Fullerenen Assoziationskonstanten beobachtet, die mit geeignet substituierten Corannulenen z.…”

Section: Calixarenkomplexeunclassified

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Bindungsmechanismen in supramolekularen Komplexen

Schneider

2009

Angewandte Chemie

185

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Kräfte‐Sammelsurium: Supramolekulare Komplexe, wie der gezeigte, beruhen meist auf einer Kombination unterschiedlichster Wechselwirkungen, wie Ionenpaarbildung, Wasserstoffbrücken und Stapelwechselwirkungen. Die nicht immer einfache Charakterisierung von Natur und Stärke der intermolekularen Kräfte liefert Beiträge zum Verständnis biomimetischer Systeme wie auch zum Design von synthetischen Rezeptoren, Wirkstoffen und intelligenten Materialien. Die supramolekulare Chemie hat in den letzten Jahren eine enorme Ausdehnung erfahren, sowohl mit Blick auf mögliche Anwendungen wie auch auf analoge biologische Systeme. Bildung und Funktion supramolekularer Komplexe werden durch eine Vielzahl von oft schwer zu differenzierenden nichtkovalenten Kräften bestimmt. Ziel dieses Aufsatzes ist es, die entscheidenden Wechselwirkungsmechanismen zusammenhängend darzustellen und das Gesamtgebiet auf diese Weise zu klassifizieren. Als Beispiele werden meist organische Wirt‐Gast‐Komplexe gewählt, unter Berücksichtigung auch von biologisch relevanten Fragestellungen. Das Verständnis und die Quantifizierung der intermolekularen Wechselwirkungen ist für die rationale Planung neuer supramolekularer Systeme, einschließlich intelligenter Materialien, ebenso von Bedeutung wie für die Entwicklung neuer Wirkstoffe.

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Section: Elektrostatische Wechselwirkungenunclassified

“…Komplexe von elektronenreichen Cleft-oder Pinzettenverbindungen mit elektronenarmen Gastmolekülen; Aktivierungsenergien des Austauschs DG* in CDCl 3 . [236] H.-J. Schneider Aufsätze…”

Section: Elektrostatische Wechselwirkungenunclassified

Section: Calixarenkomplexeunclassified

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Bindungsmechanismen in supramolekularen Komplexen

Schneider

2009

Angewandte Chemie

185

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“…Like this, they are too far apart to -stack and thus ideally placed to serve as -clamps. -Clamps, also referred to as tweezers, clips, clefts, or jaws, [79][80][81][82][83][84][85][86][87] are quite popular bifunctional acyclic hosts that form faceto-face complexes with intercalating aromatic guest (e.g., 48, Fig. 4).…”

mentioning

confidence: 99%

“…4). Different to molecular recognition by caffeine, 79 acridine, 80 phenantrene, 80 glycoluryl, 81 naphthalene, 82 anthracene, 82 pyrene, 83 porphyrin, [84][85][86] or pentafluorophenyl 87 tweezers, different also to Butterfield and Waters' pioneering tryptophan clamps on a -sheet scaffold, 88 -clamping with the ''adhesive,'' -acidic NDI dimers as such has never been studied systematically. However, the classical charge-transfer (CT) complexes with -basic dialkoxynaphthalenes (DANs) have been used extensively and successfully in supramolecular architecture.…”

mentioning

confidence: 99%

Synthetic Multifunctional Nanoarchitecture in Lipid Bilayers: Ion Channels, Sensors, and Photosystems

Bhosale

Bollot

et al. 2007

Bulletin of the Chemical Society of Japan

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The creation of functional materials such as ion channels, porous sensors, or smart photosystems depends critically on our ability to assemble sophisticated, error-free and self-repairing nanoarchitecture in a predictable manner. To address these challenging topics, we often used lipid bilayer membranes as compartmentalizing platform and have introduced rigid-rod molecules as privileged scaffolds that bypass all folding problems because they do not fold. This approach provides access to motifs such as rigid-rod barrels, helices, stacks, slides, and wires that can act as smart, stimuli-responsive photosystems, pores, ion channels, hosts, sensors, and catalysts. The selected examples focus on naphthalenediimides (NDIs), a compact, organizable, colorizable, and functionalizable n-semiconductor. This versatile module is used in rigid-rod molecules to mediate transmembrane anion transport by anion-interactions, as sticky -clamp within pore sensors to catch otherwise elusive analytes by aromatic electron donor-acceptor interactions, or in blue, transmembrane -stack architecture to collect and convert photonic energy. These specific examples with multifunctional NDI nanoarchitecture are of help to outline, on the one hand, possibilities to contribute to advanced functional materials such as multianalyte sensors or solar cells and, on the other hand, to keep on wondering about an enormous structural and functional space waiting to be explored.In biology, highest sophistication on both the structural and functional level is accomplished with membrane proteins. Ion channels and pores, for instance, function as stimuli-responsive multianalyte sensors that assure perception of and communication with the outside world.

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Complex Self‐Sorting Systems

Ghosh

2009

Dynamic Combinatorial Chemistry

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Over the past century scientists have taken a reductionist approach towards much of the physical and biological sciences. More recently scientists have become interested in constructing complex systems from their components and thereby controlling their emerging behaviors. As supramolcular chemists we have been pursuing an approach to the creation of complex functional systems -systems chemistry -by preparation of self-sorting systems. Self-sorting system displays ability to efficiently distinguish between self-and non-self even within complex mixture. This dissertation is divided into four chapters that describe increasingly complex self-sorting systems.Chapter 1 describes a literature review on self-sorting. First, we introduced the concept of self-sorting and then described the previously studied self-sorting phenomenon in the Isaacs group followed by a description of the examples of selfsorting systems in the literature.Chapter 2 describes the synthesis and characterization of eleven C-shaped methylene bridged glycoluril dimers (II-1 -II-11) bearing H-bonding groups on their aromatic rings. Compounds II-1, II-2, (±)-II-4a, (±)-II-5, and II-7 form tightly associated homodimers in CDCl 3 due to π -π and H-bonding interactions.Compounds II-2, (±)-II-5 and II-7, having disparate spatial distribution of their Hbonding groups show the ability to efficiently distinguish between self and non-self within three component mixtures in CDCl 3 . The effect of various structural modifications (e.g. chirality, side chain steric bulk, relative orientation, number and pattern of H-bonds) on the strength of self-assembly and the fidelity of self-sorting are presented.Chapter 3 describes the stepwise construction of an 8-component self-sorted system (III-1 -III-8) by the sequential addition of components. This process occurs via a large number of states (2 8 = 256) and even a larger number of pathways (8! = 40320). A pathway (III-5, III-6, III-7, III-8, III-4, III-3, III-2, then III-1) that is self-sorted at every step along the way. Another pathway (III-1, III-8, III-3, III-5, III-4, III-7, III-2, then III-6) exhibits interesting shuttling of guest molecules among hosts. The majority of pathways -unlike the special ones described above -proceed through several non self-sorted states. We characterized the remainder of the 40320 pathways by simulation using GEPASI and describe the influence of concentration, mean binding constants and standard deviation on the fidelity of the self-sorting pathways.Chapter 4 describes a method to control biological catalysis using synthetic self-sorting systems. We report the synthesis of IV-1 -IV-5 which contain both enzyme inhibitor and cucurbit[n]uril binding domains. The enzyme binding domains of IV-1 -IV-5 bind to the active sites of Bovine Carbonic Anhydrase or Acetylcholinesterase and inhibit their catalytic activities. Addition of CB [7] catalyzes the dissociation of IV-1 and IV-2 from the active site of BCA and thereby regenerates the enzymatic activity. In contrast, addition of CB [7] to...

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Molecular Tweezers and Clips as Synthetic Receptors. Molecular Recognition and Dynamics in Receptor−Substrate Complexes

Cited by 369 publications

References 36 publications

Bindungsmechanismen in supramolekularen Komplexen

Bindungsmechanismen in supramolekularen Komplexen

Synthetic Multifunctional Nanoarchitecture in Lipid Bilayers: Ion Channels, Sensors, and Photosystems

Complex Self‐Sorting Systems

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