Unprecedented gas-phase chiroselective logic gates

Botta, Bruno; Fraschetti, Caterina; D’Acquarica, Ilaria; Sacco, Fabiola; Mattay, Jochen; Letzel, Matthias C.; Speranza, Maurizio

doi:10.1039/c0ob00664e

Cited by 8 publications

(7 citation statements)

References 7 publications

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“…trans ‐1,2‐Diaminocyclohexane and (1 R ,2 R )‐ or (1 S ,2 S )‐1,2‐diphenylethylenediamine have been largely employed as the precursors of several macrocyclic chiral receptors, among which bis(diamido)‐bridged basket resorcin[4]arene (all-S)-1 (Scheme ) and its ( all‐R ) enantiomer demonstrated the ability of selectively encapsulating amino acids, chiral amines, amphetamine, and vinca alkaloids in the gaseous phase, i.e., under conditions where the phenomenon is not influenced by solvation and ion pairing effects. Interestingly, proton‐bound diastereomeric complexes of the above mentioned hosts with pyrimidine nucleosides behave as supramolecular “chiroselective logic gates” in the gas phase by releasing the nucleoside depending on the resorcin[4]arene configuration . This interesting property has been demonstrated by mass spectrometry, and, more recently, by variable‐wavelength infrared multiple photon dissociation (IRMPD), allowing differentiation of the complexes formed in the gas phase by (all-S)-1 and (all-R)-1 and selected nucleosides.…”

Section: Introductionmentioning

confidence: 99%

Stereochemical Preference of 2'‐Deoxycytidine for Chiral Bis(diamido)‐bridged Basket Resorcin[4]arenes

et al. 2013

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Bis(diamido)-bridged basket resorcin[4]arene (all-S)-1 and its (all-R)-1 enantiomer proved able to interact with 2'-deoxycytidine (2) and pyrimidine nucleoside analogs in dimethyl sulfoxide (DMSO) solution. In such a solvent, the resorcinarene hosts adopt a preferential 1,3-alternate-like conformation, with a larger cavity delimited by two syn 3,5-dimethoxyphenyl moieties, and two external pockets, each delimited by the other 3,5-dimethoxyphenyl group and its diamido arm (the wing). Complexation phenomena were investigated by nuclear magnetic resonance (NMR) methods, including (1)H NMR DOSY and 1D ROESY experiments, and molecular modeling. Heteroassociation constants of [(all-S)-1·2] and [(all-R)-1·2] diastereoisomeric complexes were obtained from diffusion data by single point measurements, and from nonlinear fitting of 1H NMR chemical shifts. Selective proton relaxation rate measurements allowed us to significantly discriminate the two complexes by identifying two different interaction sites of the guest in the resorcin[4]arene host, depending on its configuration.

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Section: Introductionmentioning

confidence: 99%

Stereochemical Preference of 2'‐Deoxycytidine for Chiral Bis(diamido)‐bridged Basket Resorcin[4]arenes

et al. 2013

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“…The more relevant result was observed for the complexes with G = dC as guest [55]. Indeed, when the host was in the R- configuration no reaction products were detected even after 300 s reaction time ([B] = 7.4 × 10 9 molecule cm −3 ), whereas, under the same experimental conditions, the reaction carried out on the [ V S ∙ H∙dC] + complex occurred and proceeded to over 20%.…”

Section: Reviewmentioning

confidence: 80%

“…Nucleosides are the elementary units of the RNA and DNA biomacromolecules, and their physiological importance at many different levels [52–54] makes them potential candidates as anticancer drugs. The gas-phase study of the intimate interactions between the resorcin[4]arene V and several pyrimidine nucleosides can be an inspiration for both the design of new drug carriers, characterized by high solubility and selectivity, and a better understanding of the selective uptake of nucleosides by their respective membrane receptors [55]. The selected pyrimidine nucleosides are reported in Fig.…”

Section: Reviewmentioning

confidence: 99%

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Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system

Fraschetti¹,

Letzel²,

Filippi³

et al. 2012

Beilstein J. Org. Chem.

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SummaryThis review describes the state-of-art in the field of the gas-phase reactivity of diastereomeric complexes formed between a chiral artificial receptor and a biologically active molecule. The presented experimental approach is a ligand-displacement reaction carried out in a nano ESI-FT-ICR instrument, supported by a thermodynamic MS-study and molecular-mechanics and molecular-dynamics (MM/MD) computational techniques. The noncovalent ion–molecule complexes are ideal for the study of chiral recognition in the absence of complicating solvent and counterion effects.

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“…Cytidine (2) and its epimer cytarabine (3) were used as chiral guests because of their ability to establish stable proton bonds with the amidocarbonyl groups on the basket resorcin [4]arene. [39][40][41] For comparison, the study was also extended to cytosine (1), which was used as a simplified achiral model of compounds 2 and 3. For the sake of clarity, the functional groups that belong to the host will be given in italic.…”

Section: Introductionmentioning

confidence: 99%

Chirality Effects on the IRMPD Spectra of Basket Resorcinarene/Nucleoside Complexes

Filippi

Fraschetti

Piccirillo

et al. 2012

Chemistry A European J

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The IRMPD spectra of the ESI‐formed proton‐bound complexes of the R,R,R,R‐ and S,S,S,S‐enantiomers of a bis(diamido)‐bridged basket resorcin[4]arene (R and S) with cytosine (1), cytidine (2), and cytarabine (3) were measured in the region 2800–3600 cm−1. Comparison of the IRMPD spectra with the corresponding ONIOM (B3LYP/6‐31(d):UFF)‐calculated absorption frequencies allowed the assessment of the vibrational modes that are responsible for the observed spectroscopic features. All of the complexes investigated, apart from [R⋅H⋅3]+, showed similar IRMPD spectra, which points to similar structural and conformational landscapes. Their IRMPD spectra agree with the formation of several isomeric structures in the ESI source, wherein the N(3)‐protonated guest establishes noncovalent interactions with the host amidocarbonyl groups that are either oriented inside the host cavity or outside it between one of the bridged side‐chains and the upper aromatic nucleus. The IRMPD spectrum of the [R⋅H⋅3]+ complex was clearly different from the others. This difference is attributed to the effect of intramolecular hydrogen‐bonding interactions between the C(2′)OH group and the aglycone oxygen atom of the nucleosidic guest upon repulsive interactions between the same oxygen atom and the aromatic rings of the host.

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Unprecedented gas-phase chiroselective logic gates

Abstract: The gas-phase encounters between 2-aminobutane and proton-bound chiral resorcin[4]arene/nucleoside complexes behave in the gas phase as supramolecular "chiroselective logic gates" by releasing the nucleoside depending on the resorcin[4]arene and the 2-aminobutane configurations.

Cited by 8 publications

References 7 publications

Stereochemical Preference of 2'‐Deoxycytidine for Chiral Bis(diamido)‐bridged Basket Resorcin[4]arenes

Stereochemical Preference of 2'‐Deoxycytidine for Chiral Bis(diamido)‐bridged Basket Resorcin[4]arenes

Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system

Chirality Effects on the IRMPD Spectra of Basket Resorcinarene/Nucleoside Complexes

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