Supplementary data for article: Chen, S.; Ruan, Y.; Brown, J. D.; Gallucci, J.; Maslak, V.; Hadad, C. M.; Bađić, J. D. Assembly of Amphiphilic Baskets into Stimuli-Responsive Vesicles. Developing a Strategy for the Detection of Organophosphorus Chemical Nerve Agents. Journal of the American Chemical Society 2013, 135 (40), 14964–14967. https://doi.org/10.1021/ja408585j

Supporting information for: [https://doi.org/10.1021/ja408585j]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1427

Supplementary data for article: Ruan, Y.; Taha, H. A.; Yoder, R. J.; Maslak, V.; Hadad, C. M.; Bađić, J. 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. Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys 2013, 117 (11), 3240–3249. https://doi.org/10.1021/jp401841w

Supporting information for: [https://doi.org/10.1021/jp401841w]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1619

Supplementary material for the article: Mitrović, A.; Stevanović, J.; Milčić, M.; Žekić, A.; Stanković, D.; Chen, S.; Badjić, J. D.; Milić, D.; Maslak, V. Fulleropyrrolidine Molecular Dumbbells Act as Multi-Electron-Acceptor Triads. Spectroscopic, Electrochemical, Computational and Morphological Characterizations. RSC Advances 2015, 5 (107), 88241–88248. https://doi.org/10.1039/c5ra16309a

Supplementary material for:[https://doi.org/10.1039/c5ra16309a]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1984

Supplementary data for article: Chen, S.; Ruan, Y.; Brown, J. D.; Gallucci, J.; Maslak, V.; Hadad, C. M.; Bađić, J. D. Assembly of Amphiphilic Baskets into Stimuli-Responsive Vesicles. Developing a Strategy for the Detection of Organophosphorus Chemical Nerve Agents. Journal of the American Chemical Society 2013, 135 (40), 14964–14967. https://doi.org/10.1021/ja408585j

Supporting information for: [https://doi.org/10.1021/ja408585j]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1427

Supplementary data for article: Ruan, Y.; Taha, H. A.; Yoder, R. J.; Maslak, V.; Hadad, C. M.; Bađić, J. 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. Journal of Physical Chemistry. Part B: Condensed Matter, Materials, Surfaces, Interfaces and Biophys 2013, 117 (11), 3240–3249. https://doi.org/10.1021/jp401841w

Supporting information for: [https://doi.org/10.1021/jp401841w]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1619

Supplementary material for the article: Mitrović, A.; Stevanović, J.; Milčić, M.; Žekić, A.; Stanković, D.; Chen, S.; Badjić, J. D.; Milić, D.; Maslak, V. Fulleropyrrolidine Molecular Dumbbells Act as Multi-Electron-Acceptor Triads. Spectroscopic, Electrochemical, Computational and Morphological Characterizations. RSC Advances 2015, 5 (107), 88241–88248. https://doi.org/10.1039/c5ra16309a

Supplementary material for:[https://doi.org/10.1039/c5ra16309a]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1984

Allosteric regulation of the conformational dynamics of a cavitand receptor

Inspired by allostery in nature, we synthesized cavitand 1 and investigated regulation of its conformational dynamics. Quantitative H-1 NMR studies have revealed that the rate of the conformational isomerization of 1 can be modulated using the external addition of acid. As 1 maintains its vase-like conformation in an acidic environment, ample opportunities for controlling the kinetics of molecular recognition, and thus reactivity, in this and related receptors have arisen

A 3-fold "Butterfly Valve" in Command of the Encapsulation's Kinetic Stability. Molecular Baskets at Work

Molecular basket 1, composed of a semirigid tris-norbornadiene framework and three revolving pyridine-based gates at the rim, has been built to "dynamically" enclose space and as such regulate molecular encapsulation. The gates were shown to fold via intramolecular hydrogen bonding and thereby form a G(3v) symmetrical receptor: the (1)H NMR resonance for the amide N-H protons of the pyridine gates appeared downfield (delta = 10.98 ppm), and the N-H vibrational stretch (IR) was observed at 3176 cm(-1). Accordingly, density functional theory (DFT, B3LYP) investigations revealed for the closed conformers of 1 to be energetically the most stable and dominant. The gearing of the pyridine "gates", about their axis, led to the interconversion of two dynamic enantiomers 1(A) and 1(B) comprising the clockwise and counterclockwise seam of intramolecular hydrogen bonds. Dynamic (1)H NMR spectroscopic measurements and line-shape simulations suggested that the energy barrier of 10.0 kcal/mol (Delta G(A/B)(double dagger), 298 K) is required for the 1(A/B) interconversion, when CCl(4) occupies the cavity of 1. Likewise, the activation free energy for CCl4 departing the basket was found to be 13.1 kcal/mol (Delta G(double dagger), 298 K), whereas the thermodynamic stability of 1:CCl(4) complex was -2.7 kcal/mol (Delta G degrees, 298 K). In view of that, CCI4 (but also (CH(3))(3)CBr) was proposed to escape from, and a molecule of solvent to enter, the basket when the gates rotate about their axis: the exit of CCl(4) requires the activation energy of 12.7 kcal/mol (Delta G(A/B)(double dagger) + Delta G degrees), similar to the experimentally found 13.1 kcal/mol (Delta G(double dagger))

Supramolecular catalysis at work: Diastereoselective synthesis of a molecular bowl with dynamic inner space

[GRAPHICS] The supramolecular assistance to Pd(0)/Cu(I)-catalyzed cyclotrimerization of stannylated norbornene 7 has been investigated to give molecular bowl 1(syn) in a stereoselective fashion. Following a divergent strategy, racemic norbornene 7 was synthesized in satisfactory yield. Self-coupling, promoted by Pd(0)/Cu(I) catalysis acting in synergy with CsF, yielded molecular bowl 1(syn) in a moderate 30% yield. The reaction diastereoselectivity is affected by the concentration of Cu(I) and Cs+: increasing quantities of the cations enhanced the synlanti ratio of the isolated cyclotrimer from statistical (1:3) to a more desirable (4.5:1) ratio, in favor of the molecular bowl 1(syn) H-1 NMR spectroscopic studies suggested the coordinating affinity of 1(syn) toward transition metals Cu(I), Ag(I), and Au(I), to account for the observed templation effect. In particular, the tridentate 1(syn) has been shown to bind to one Ag(I) cation in the assembly process that is driven with enthalpy (Delta H-0 = - 19 +/- 2 kcal/mol, Delta S-0 = -45 eu). The complete coordination was not cooperative, and was hypothesized to be impeded with the adverse entropy. Accordingly, density functional theory (BP86) calculations of 1(syn) and its mono-, bis-, and tris-Ag(I) complexes suggested that the coordination of one to three silver cations is highly exothermic. The calculations also revealed that the bowl constriction is necessary for the aromatic arms to become preorganized and bind to a silver cation(s) (Delta E approximate to 8 kcal/mol). Ultimately, Ag(I) has been shown to assist the diastereoselective formation of lending support to the notion, of template-directed synthesis