The Prospect of Selective Recognition of Nerve Agents with Modular Basket-like Hosts. A Structure-Activity Study of the Entrapment of a Series of Organophosphonates in Aqueous Media
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2013
Authors
Ruan, YianTaha, Hashem A.
Yoder, Ryan J.
Maslak, Veselin
Hadad, Christopher M.
Bađić, Jovica D.
Article (Published version)
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We designed, prepared, and characterized three cup-shaped cavitands 1-3 for trapping organophosphonates (O=PR(OR')(2), 118-197 A3) whose shape and size correspond to G-type chemical warfare agents (132-186 A(3)). With the assistance of computational (molecular dynamics) and experimental CH NMR spectroscopy) methods, we found that host [1-H-3](3+) orients its protonated histamine residues at the rim outside the cavity, in bulk water. In this unfolded form, the cavitand traps a series of organophosphonates 5-13 (K-app = 87 +/- 1 to 321 +/- 6 M-1 at 298.0 K), thereby placing the P-CH3 functional group in the inner space of the host. A comparison of experimental and computed H-1 NMR chemical shifts of both hosts and guests allowed us to derive structure activity relationships and deduce that, upon the complexation, the more sizable P OR functional groups in guests drive organophosphonates to the northern portion of the basket [1-H-3](3+). This, in turn, causes a displacement of the guest's... P-CH3 group and a contraction of the cupshaped scaffold. The proposed induced-fit model of the recognition is important for turning these modular hosts into useful receptors capable of a selective detection/degradation of organophosphorus nerve agents.
Source:
Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys, 2013, 117, 11, 3240-3249Publisher:
- Amer Chemical Soc, Washington
Funding / projects:
- Department of Defense, Defense Threat Reduction Agency [HDTRA1-11-1-0042]
- National Science Foundation [CHE-1012146]
Note:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3556
DOI: 10.1021/jp401841w
ISSN: 1520-6106
PubMed: 23445375
WoS: 000316773300020
Scopus: 2-s2.0-84875460443
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Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Ruan, Yian AU - Taha, Hashem A. AU - Yoder, Ryan J. AU - Maslak, Veselin AU - Hadad, Christopher M. AU - Bađić, Jovica D. PY - 2013 UR - https://cherry.chem.bg.ac.rs/handle/123456789/1619 AB - We designed, prepared, and characterized three cup-shaped cavitands 1-3 for trapping organophosphonates (O=PR(OR')(2), 118-197 A3) whose shape and size correspond to G-type chemical warfare agents (132-186 A(3)). With the assistance of computational (molecular dynamics) and experimental CH NMR spectroscopy) methods, we found that host [1-H-3](3+) orients its protonated histamine residues at the rim outside the cavity, in bulk water. In this unfolded form, the cavitand traps a series of organophosphonates 5-13 (K-app = 87 +/- 1 to 321 +/- 6 M-1 at 298.0 K), thereby placing the P-CH3 functional group in the inner space of the host. A comparison of experimental and computed H-1 NMR chemical shifts of both hosts and guests allowed us to derive structure activity relationships and deduce that, upon the complexation, the more sizable P OR functional groups in guests drive organophosphonates to the northern portion of the basket [1-H-3](3+). This, in turn, causes a displacement of the guest's P-CH3 group and a contraction of the cupshaped scaffold. The proposed induced-fit model of the recognition is important for turning these modular hosts into useful receptors capable of a selective detection/degradation of organophosphorus nerve agents. PB - Amer Chemical Soc, Washington T2 - Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys T1 - The Prospect of Selective Recognition of Nerve Agents with Modular Basket-like Hosts. A Structure-Activity Study of the Entrapment of a Series of Organophosphonates in Aqueous Media VL - 117 IS - 11 SP - 3240 EP - 3249 DO - 10.1021/jp401841w ER -
@article{ author = "Ruan, Yian and Taha, Hashem A. and Yoder, Ryan J. and Maslak, Veselin and Hadad, Christopher M. and Bađić, Jovica D.", year = "2013", abstract = "We designed, prepared, and characterized three cup-shaped cavitands 1-3 for trapping organophosphonates (O=PR(OR')(2), 118-197 A3) whose shape and size correspond to G-type chemical warfare agents (132-186 A(3)). With the assistance of computational (molecular dynamics) and experimental CH NMR spectroscopy) methods, we found that host [1-H-3](3+) orients its protonated histamine residues at the rim outside the cavity, in bulk water. In this unfolded form, the cavitand traps a series of organophosphonates 5-13 (K-app = 87 +/- 1 to 321 +/- 6 M-1 at 298.0 K), thereby placing the P-CH3 functional group in the inner space of the host. A comparison of experimental and computed H-1 NMR chemical shifts of both hosts and guests allowed us to derive structure activity relationships and deduce that, upon the complexation, the more sizable P OR functional groups in guests drive organophosphonates to the northern portion of the basket [1-H-3](3+). This, in turn, causes a displacement of the guest's P-CH3 group and a contraction of the cupshaped scaffold. The proposed induced-fit model of the recognition is important for turning these modular hosts into useful receptors capable of a selective detection/degradation of organophosphorus nerve agents.", publisher = "Amer Chemical Soc, Washington", journal = "Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys", title = "The Prospect of Selective Recognition of Nerve Agents with Modular Basket-like Hosts. A Structure-Activity Study of the Entrapment of a Series of Organophosphonates in Aqueous Media", volume = "117", number = "11", pages = "3240-3249", doi = "10.1021/jp401841w" }
Ruan, Y., Taha, H. A., Yoder, R. J., Maslak, V., Hadad, C. M.,& Bađić, J. D.. (2013). The Prospect of Selective Recognition of Nerve Agents with Modular Basket-like Hosts. A Structure-Activity Study of the Entrapment of a Series of Organophosphonates in Aqueous Media. in Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys Amer Chemical Soc, Washington., 117(11), 3240-3249. https://doi.org/10.1021/jp401841w
Ruan Y, Taha HA, Yoder RJ, Maslak V, Hadad CM, Bađić JD. The Prospect of Selective Recognition of Nerve Agents with Modular Basket-like Hosts. A Structure-Activity Study of the Entrapment of a Series of Organophosphonates in Aqueous Media. in Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys. 2013;117(11):3240-3249. doi:10.1021/jp401841w .
Ruan, Yian, Taha, Hashem A., Yoder, Ryan J., Maslak, Veselin, Hadad, Christopher M., Bađić, Jovica D., "The Prospect of Selective Recognition of Nerve Agents with Modular Basket-like Hosts. A Structure-Activity Study of the Entrapment of a Series of Organophosphonates in Aqueous Media" in Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys, 117, no. 11 (2013):3240-3249, https://doi.org/10.1021/jp401841w . .