Dataset Information

The Nature of Interactions and UV-Induced Response within α-Zirconium Phosphate Intercalation Compounds with Azobenzenes.

ABSTRACT: Azobenzenes immobilization on a solid support enables the usage of their trans-cis isomerization ability for preparation of functional materials. The behavior of azobenzenes in the interlayer space of α-zirconium phosphate (ZrP) upon the UV-Vis irradiation was investigated. Two experimental approaches were performed: (1) co-intercalation of benzylalkylammonium surfactants and azobenzene in the interlayers of ZrP (ZBCnA), and (2) intercalation of p-aminoazobenzene (ZpA). The materials were characterized with XRD, FTIR, UV-Vis, CHN analysis, and the molecular modeling. The molecules in ZBCnA samples were sparsely packed and held by weak hydrophobic interactions. Conversely, the molecules in ZpA sample were strongly H-bonded to the ZrP, well-ordered, and densely packed. These structural features determined the samples' photoresponsive behavior. Low density of molecules in the ZBCnA samples, allowed the effective, fast, and reversible isomerization of azobenzene. Whereas the ZpA sample did not react to the UV irradiation because of the steric hindrance of tightly packed molecules.

SUBMITTER: Koteja A

PROVIDER: S-EPMC6539894 | biostudies-other | 2019 May

REPOSITORIES: biostudies-other

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The Nature of Interactions and UV-Induced Response within α-Zirconium Phosphate Intercalation Compounds with Azobenzenes.

Koteja Anna A Matusik Jakub J Luberda-Durnaś Katarzyna K Szczerba Marek M

Materials (Basel, Switzerland) 20190502 9

Azobenzenes immobilization on a solid support enables the usage of their trans-cis isomerization ability for preparation of functional materials. The behavior of azobenzenes in the interlayer space of α-zirconium phosphate (ZrP) upon the UV-Vis irradiation was investigated. Two experimental approaches were performed: (1) co-intercalation of benzylalkylammonium surfactants and azobenzene in the interlayers of ZrP (ZBCnA), and (2) intercalation of p-aminoazobenzene (ZpA). ...[more]

PMID: 31052552

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Project description:Phosphoryl transfer plays key roles in signaling, energy transduction, protein synthesis, and maintaining the integrity of the genetic material. On the surface, it would appear to be a simple nucleophile displacement reaction. However, this simplicity is deceptive, as, even in aqueous solution, the low-lying d-orbitals on the phosphorus atom allow for eight distinct mechanistic possibilities, before even introducing the complexities of the enzyme catalyzed reactions. To further complicate matters, while powerful, traditional experimental techniques such as the use of linear free-energy relationships (LFER) or measuring isotope effects cannot make unique distinctions between different potential mechanisms. A quarter of a century has passed since Westheimer wrote his seminal review, 'Why Nature Chose Phosphate' (Science 235 (1987), 1173), and a lot has changed in the field since then. The present review revisits this biologically crucial issue, exploring both relevant enzymatic systems as well as the corresponding chemistry in aqueous solution, and demonstrating that the only way key questions in this field are likely to be resolved is through careful theoretical studies (which of course should be able to reproduce all relevant experimental data). Finally, we demonstrate that the reason that nature really chose phosphate is due to interplay between two counteracting effects: on the one hand, phosphates are negatively charged and the resulting charge-charge repulsion with the attacking nucleophile contributes to the very high barrier for hydrolysis, making phosphate esters among the most inert compounds known. However, biology is not only about reducing the barrier to unfavorable chemical reactions. That is, the same charge-charge repulsion that makes phosphate ester hydrolysis so unfavorable also makes it possible to regulate, by exploiting the electrostatics. This means that phosphate ester hydrolysis can not only be turned on, but also be turned off, by fine tuning the electrostatic environment and the present review demonstrates numerous examples where this is the case. Without this capacity for regulation, it would be impossible to have for instance a signaling or metabolic cascade, where the action of each participant is determined by the fine-tuned activity of the previous piece in the production line. This makes phosphate esters the ideal compounds to facilitate life as we know it.

Dataset Information

The Nature of Interactions and UV-Induced Response within α-Zirconium Phosphate Intercalation Compounds with Azobenzenes.

Publications

The Nature of Interactions and UV-Induced Response within α-Zirconium Phosphate Intercalation Compounds with Azobenzenes.

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