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Conformation of intrazeolitic choline ions and the framework topology of zeolite hosts.

ABSTRACT: The host-guest interactions in as-made zeolites Y, UZM-4, UZM-22, offretite, ferrierite, phillipsite, EU-12 and levyne, all of which were synthesized using choline as an organic structure-directing agent, have been investigated by a combination of different experimental techniques, including Raman, ¹H-¹³C CP MAS NMR and variable-temperature IR spectroscopies, together with theoretical calculations. The conformation of this asymmetric quaternary ammonium cation was shown to differ significantly according to the pore topology of the zeolite host and the intrazeolitic location of the organic guest molecule. Theoretical calculations using the pure-silica zeolite model reveal that among its three representative conformers (i.e., gauche, trans and trans' forms), the conformer, which was experimentally found to dominantly or exclusively exist in zeolite structures studied, always has a lower interaction energy with the surrounding zeolite framework. Our work provides the first example in which the conformation of organic structure-directing agents plays an important kinetic role in governing the phase selectivity during zeolite nucleation.

SUBMITTER: Bae J

PROVIDER: S-EPMC6194500 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Conformation of intrazeolitic choline ions and the framework topology of zeolite hosts.

Bae Juna J Hong Suk Bong SB

Chemical science 20180820 40

The host-guest interactions in as-made zeolites Y, UZM-4, UZM-22, offretite, ferrierite, phillipsite, EU-12 and levyne, all of which were synthesized using choline as an organic structure-directing agent, have been investigated by a combination of different experimental techniques, including Raman, <sup>1</sup>H-<sup>13</sup>C CP MAS NMR and variable-temperature IR spectroscopies, together with theoretical calculations. The conformation of this asymmetric quaternary ammonium cation was shown to ...[more]

PMID: 30429987

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Project description:ConspectusCarbohydrates (glycans, saccharides, and sugars) are essential molecules in all domains of life. Research on glycoscience spans from chemistry to biomedicine, including material science and biotechnology. Access to pure and well-defined complex glycans using synthetic methods depends on the success of the employed glycosylation reaction. In most cases, the mechanism of the glycosylation reaction is believed to involve the oxocarbenium ion. Understanding the structure, conformation, reactivity, and interactions of this glycosyl cation is essential to predict the outcome of the reaction. In this Account, building on our contributions on this topic, we discuss the theoretical and experimental approaches that have been employed to decipher the key features of glycosyl cations, from their structures to their interactions and reactivity.We also highlight that, from a chemical perspective, the glycosylation reaction can be described as a continuum, from unimolecular SN1 with naked oxocarbenium cations as intermediates to bimolecular SN2-type mechanisms, which involve the key role of counterions and donors. All these factors should be considered and are discussed herein. The importance of dissociative mechanisms (involving contact ion pairs, solvent-separated ion pairs, solvent-equilibrated ion pairs) with bimolecular features in most reactions is also highlighted.The role of theoretical calculations to predict the conformation, dynamics, and reactivity of the oxocarbenium ion is also discussed, highlighting the advances in this field that now allow access to the conformational preferences of a variety of oxocarbenium ions and their reactivities under SN1-like conditions.Specifically, the ground-breaking use of superacids to generate these cations is emphasized, since it has permitted characterization of the structure and conformation of a variety of glycosyl oxocarbenium ions in superacid solution by NMR spectroscopy.We also pay special attention to the reactivity of these glycosyl ions, which depends on the conditions, including the counterions, the possible intra- or intermolecular participation of functional groups that may stabilize the cation and the chemical nature of the acceptor, either weak or strong nucleophile. We discuss recent investigations from different experimental perspectives, which identified the involved ionic intermediates, estimating their lifetimes and reactivities and studying their interactions with other molecules. In this context, we also emphasize the relationship between the chemical methods that can be employed to modulate the sensitivity of glycosyl cations and the way in which glycosyl modifying enzymes (glycosyl hydrolases and transferases) build and cleave glycosidic linkages in nature. This comparison provides inspiration on the use of molecules that regulate the stability and reactivity of glycosyl cations.

Dataset Information

Conformation of intrazeolitic choline ions and the framework topology of zeolite hosts.

Publications

Conformation of intrazeolitic choline ions and the framework topology of zeolite hosts.

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