Noncovalent complexation of glucosylthioureidocalix[4]arenes with carboxylates and their gas‐phase characteristics: an ESI‐FTICR mass spectrometric study

The cation binding strength of calix[4]pyrroles in the gas phase has been evaluated by computational studies and further substantiated by ESI mass spectrometry experiments. The DFT optimized geometries of [CP + X](+) complexes are found to be stable in a 1,3-alternate conformation through cation-π interactions and interestingly CPs are found to be better cation receptor than calix[4]arenes. The binding energy values of [CP + X](+) complexes computed at B2PLYP/TZVP//M05-2X/TZVP follows the binding order, Li(+) > Na(+) > K(+) > Rb(+) > Cs(+). The diameter of Li(+) matches very well with the cavity size of CP and thus is optimally disposed to interact simultaneously with all four pyrrole rings through multiple cation-π interactions. However, other cations, due to the increase in their size, drift away from the cavity center towards the rim of the cavity exhibiting weak cation-π interactions. Energy decomposition analysis (EDA) reveals that the electrostatic and polarization effects act as the major driving force in these interactions. The important outcome of the current study is that the stability of precursor and product ions is found to be crucial in the experimental evaluation of binding affinity of Li(+) and Na(+) complexes of CP. The ESI-MS/MS experiments on the cation complexes of different substituted CPs revealed that the binding strength of CPs towards cations is also dependant on the substituents at the meso-position.

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“…4 30 CE value and dissociation curves were drawn. 31 The typical curves obtained for the studied metal ions were shown in Fig. S7.…”

Section: Resultsmentioning

confidence: 99%

“…The relative intensity (%) values of [CP + X] + were calculated at each CE value and dissociation curves were drawn. 31 The typical curves obtained for the studied metal ions were shown in Fig. S7 (ESI †).…”

Section: Complexesmentioning

confidence: 99%

Evaluating the cation binding strength and selectivity of calix[4]pyrroles: a computational and ESI-MS/MS study

Kumar

Sharma

Soujanya

et al. 2014

Phys. Chem. Chem. Phys.

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“…The selectivity for isophthalate over phthalate and terephthalate or for fumarate over maleate is remarkable, indicating that these hosts prefer guests with suitably located H-bond acceptor groups. 54 The conformationally mobile derivative 25a was also used in a study focused on a series of monoamine neurotransmitters of relevant interest for neurodegenerative pathologies, such as schizophrenia and Parkinson's or Alzheimer's diseases. Interestingly these guests are complexed as ammonium ions in the gas phase demonstrating the dual behaviour of the glycocalixarene acting as a host for both the anions and ammonium ions.…”

Section: Glycocalixarenes and Multitaskingmentioning

confidence: 99%

Multivalent glycocalixarenes for recognition of biological macromolecules: glycocalyx mimics capable of multitasking

2013

Self Cite

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The glycoside cluster effect, a special case of multivalency involving carbohydrates, is a powerful tool exploited by Nature to make relatively weak interactions stronger and more specific. Organic and supramolecular chemists have been applying this concept and are devising a plethora of neo-glycoconjugates which can interfere with a series of pathological events such as infections due to viruses and bacteria, tumour progression and migration, and inflammation processes. In the present Tutorial Review, we will illustrate the factors that make calixarenes, the cyclic oligomers obtained by the condensation of phenols/resorcinols and aldehydes, unique scaffolds for the construction of multivalent glycosylated ligands, individually analysing how structural parameters such as the size, valency, conformation, self-assembling behaviour of the macrocycle and especially the topology of the saccharide presentation in space influence the biological properties. We will not only survey the most significant results obtained to date in the inhibition of carbohydrate binding proteins (lectins), but we will also try to paint a picture of the potential that multivalent glycocalixarenes might have in bionanotechnology and nanomedicine, that are especially related to their combined ability to load cargo and to specifically deliver that cargo to target cells.

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“…Series of thiourea-linked calix [4]arene glycoclusters [50][51][52] have been synthesized and their interactions with proteins [53][54][55][56][57], anionic species [57], natural amino acids [52], and carboxylates [58] investigated. Possible cooperation between the aromatic cavity, thiourea linkers, and sugar units of glucosylcalixarenes in the guest binding has been indicated in these studies [57].…”

Section: Introductionmentioning

confidence: 99%

“…Clear selectivity towards aromatic amino acids has also been observed, and enhanced by the introduction of an additional hydrogen bonding group to the amino acid side chain [52]. The proximity of the hydrogen bonding groups of the guest also has a major effect on the selectivity of the complexation [58].…”

Section: Introductionmentioning

confidence: 99%

Noncovalent Complexation of Monoamine Neurotransmitters and Related Ammonium Ions by Tetramethoxy Tetraglucosylcalix[4]arene

Torvinen

Kalenius

Sansone

et al. 2011

J. Am. Soc. Mass Spectrom.

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The noncovalent complexation of monoamine neurotransmitters and related ammonium and quaternary ammonium ions by a conformationally flexible tetramethoxy glucosylcalix[4]arene was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. The glucosylcalixarene exhibited highest binding affinity towards serotonin, norepinephrine, epinephrine, and dopamine. Structural properties of the guests, such as the number, location, and type of hydrogen bonding groups, length of the alkyl spacer between the ammonium head-group and the aromatic ring structure, and the degree of nitrogen substitution affected the complexation. Competition experiments and guest-exchange reactions indicated that the hydroxyl groups of guests participate in intermolecular hydrogen bonding with the glucocalixarene.

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Noncovalent complexation of glucosylthioureidocalix[4]arenes with carboxylates and their gas‐phase characteristics: an ESI‐FTICR mass spectrometric study

Cited by 7 publications

References 41 publications

Evaluating the cation binding strength and selectivity of calix[4]pyrroles: a computational and ESI-MS/MS study

Evaluating the cation binding strength and selectivity of calix[4]pyrroles: a computational and ESI-MS/MS study

Multivalent glycocalixarenes for recognition of biological macromolecules: glycocalyx mimics capable of multitasking

Noncovalent Complexation of Monoamine Neurotransmitters and Related Ammonium Ions by Tetramethoxy Tetraglucosylcalix[4]arene

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