Toward an Allosteric Metallated Container

Szelke, H.; Wadepohl, Hubert; Abu‐Youssef, Morsy A. M.; Krämer, Roland

doi:10.1002/ejic.200800659

Cited by 6 publications

(14 citation statements)

References 30 publications

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“…The synthetic approach to access trialkyl‐substituted carbonyl‐centered triphenylamine‐trisamides (TPAs) and tripyridylamine‐trisamides (TPyAs) is depicted in Scheme . The carboxylic acid precursors were synthesized by using procedures described in literature . The amide coupling was performed with both achiral dodecylamine ( A‐TPA and A‐TPyA ) and chiral ( S )‐3,7‐dimethyloctylamine ( S ‐TPA and S ‐TPyA ).…”

Section: Resultsmentioning

confidence: 99%

“…TPAs were obtained by first converting the tricarboxylic triacid into the triacid trichloride using oxalyl chloride, followed by coupling to the desired amines (dodecylamine and ( S )‐3,7‐dimethyloctylamine) . For the TPyAs, in contrast, the acyl chloride intermediate was unstable and therefore the amide coupling was achieved by activation of the triacid by CDI coupling . After purification by column chromatography and recrystallization, all TPAs and TPyAs were obtained in high purity as verified by 1 H and 13 C NMR spectroscopy and MALDI‐TOF‐MS.…”

Section: Resultsmentioning

confidence: 99%

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Unravelling the Pathway Complexity in Conformationally Flexible N‐Centered Triarylamine Trisamides

Adelizzi

Filot

Palmans

et al. 2016

Chemistry A European J

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Two families of C 3‐symmetrical triarylamine‐trisamides comprising a triphenylamine‐ or a tri(pyrid‐2‐yl)amine core are presented. Both families self‐assemble in apolar solvents via cooperative hydrogen‐bonding interactions into helical supramolecular polymers as evidenced by a combination of spectroscopic measurements, and corroborated by DFT calculations. The introduction of a stereocenter in the side chains biases the helical sense of the supramolecular polymers formed. Compared to other C 3‐symmetrical compounds, a much richer self‐assembly landscape is observed. Temperature‐dependent spectroscopy measurements highlight the presence of two self‐assembled states of opposite handedness. One state is formed at high temperature from a molecularly dissolved solution via a nucleation–elongation mechanism. The second state is formed below room temperature through a sharp transition from the first assembled state. The change in helicity is proposed to be related to a conformational switch of the triarylamine core due to an equilibrium between a 3:0 and a 2:1 conformation. Thus, within a limited temperature window, a small conformational twist results in an assembled state of opposite helicity.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Unravelling the Pathway Complexity in Conformationally Flexible N‐Centered Triarylamine Trisamides

Adelizzi

Filot

Palmans

et al. 2016

Chemistry A European J

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“…The use of 2,2'-bipyridines or similar chelating ligands that undergo significant conformational changes upon coordination to (transition) metal ion as a molecular hinge (or allosteric center) [60] can also be used to achieve heterotropic negatively cooperative binding as already demonstrated by the pioneering work of Rebek, Jr. depicted in Scheme 1. [63] Nabeshima and co-workers also found a general significant weaker binding of alkali metal ions in his metallacrown ether Cu + ·27 compared to the non-metallated receptor. [61,62] Using the approach to form crown ether or cryptand-like structures upon coordination of a transition metal ion to pe-ripheral 2,2'-bipyridines could also be demonstrated to result in negatively cooperative allosteric ionophores (Scheme 21).…”

Section: Heterotropic Positively Cooperative Binding Of Other Cationsmentioning

confidence: 90%

“…He also developed a number of allosteric receptors (60)(61)(62)(63)(64) for the recognition of carbohydrates that bind mono-or disaccharides via formation of boronic acid esters. [100][101][102][103][104][105][106] Schemes 43 and 44 show a selection of these heterotropic positively or negatively cooperative systems developed between 1994 and 1999 that use either crown ethers, [100,102,103] 2,2'-bipyridines, [101,104,105] or salen ligands [106] as allosteric centers.…”

Section: Heterotropic Positively Cooperative Binding Of Neutral Molecmentioning

confidence: 99%

Artificial Allosteric Receptors

Kremer¹,

Lützen²

2013

Chemistry A European J

132

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Cooperative effects in the binding of two or more substrates to different binding sites of a receptor that are a result of a conformational change caused by the binding of the first substrate--also referred to as the effector--are called allosteric effects. In biological systems, allosteric regulation is a widely used mechanism to control the function of proteins and enzymes in cellular metabolism. Inspired by this a lot of efforts have been made in supramolecular chemistry to implement this concept into artificial systems to control functions as molecular recognition, signal amplification, or even reactivity and catalysis. This review gives an up-to-date overview over the different approaches that have been reported ever since the first examples from the late 1970s/early 1980s. It covers both homo- and heterotropic examples and is divided according to the nature of the effector--cationic, anionic, or neutral--effectors and systems that use combinations of those.

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“…The ligand N-(6-aminohexyl)-4¢-methyl-2,2¢-bipyridine-4-carboxamide hydrochlorid (1) was synthesized starting from 4,4¢-dimethyl-bipyridin (Fluka) as described in the literature. 10 Stock solutions of the ligands and the metal salt were prepared with a concentration of 10 mM in bidistilled water. Stock solutions of the sulfated glycosaminoglycans were prepared with a concentration of 1 mg ml -1 .…”

Section: Experimental Generalmentioning

confidence: 99%