Homodimerization driven self-assembly of glycoluril molecular clips with covalently immobilized poly(ε-caprolactone)

Gosecka, Monika; Urbaniak, Malgorzata; Mikina, Maciej; Gosecki, Mateusz; Różański, Artur

doi:10.1039/c8sm01777h

Cited by 8 publications

(6 citation statements)

References 16 publications

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“…These glycoluril clips completely differ in the aspect of homodimerization abilities (Figure S3). Clip 2 exhibits concentration-dependent and thermosensitive behavior of monomer-dimer exchange ,, (Figures S4–S7), whereas for clip 1 the monomer state is favorable independent of its concentration and temperature (Figures S8–S11).…”

Section: Resultsmentioning

confidence: 99%

“…The self-sorting homodimerization and selective host–guest complexation with dihydroxyaromatics of glycoluril clips attracted considerable attention of researchers to tailor novel cross-linked supramolecular materials based on the glycoluril clip homodimers. , Recently, Gosecki et al demonstrated the formation of the first 3D polymer network based on the cross-links built from glycoluril clip homodimers, which were selectively degraded in the presence of resorcinol molecules . For the network construction, a polymer bearing glycoluril clips, equipped with N -(4-methoxyphenyl)isonicotinamide aromatic sidewalls oriented in the same direction along the glycoluril, was applied.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Glycoluril Molecular Clip Isomerization on the Mechanisms of Resorcinol Molecule Complexation

et al. 2020

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Supramolecular motifs showing chemoresponsive properties toward organic molecules are sought after. Their selectivity, however, may depend even on a small structural change. Here, we demonstrate the influence of isomerization of glycoluril molecular clips, equipped with N-(4-methoxyphenyl)isonicotinamide sidewalls, on the complexation of resorcinol. Concentration-and temperature-dependent 1 H NMR and 1 H− 1 H ROESY NMR experiments along with theoretical studies were employed to determine the detailed mechanisms and thermodynamic parameters of complexation for both isomers with resorcinol. This study shows that clip 1, equipped with N-(4methoxyphenyl)isonicotinamide moieties oppositely directed along the glycoluril frame, is able to associate one resorcinol molecule within its cleft according to the "inner" mechanism with the equilibrium constant, K 283K = 2340 M −1 . Within the clip cleft, resorcinol forms hydrogen bonds via OH groups with oxygen atoms of clip's urea moieties and interacts with clip aromatic sidewalls via π−π stacking. Clip 2, the isomer whose N-(4-methoxyphenyl)isonicotinamide moieties are oriented in the same direction along the glycoluril core, possesses two binding sites and complexes resorcinol according to 1:2 stoichiometry. One of the binding sites is located in the clip cleft analogous to clip 1, whereas the second one is created by the mutual arrangement of pyridinyl moieties. The distance between nitrogen groups of individual pyridine moieties matches the distance of resorcinol hydroxyl groups facilitating the formation of two hydrogen bonds according to the "outer" mechanism. Both mechanisms are spontaneous (ΔG 11 and ΔG 12 < 0); however, the association constant differs, that is, K 11 = 2520 M −1 and K 12 = 650 M −1 at 283 K. Both mechanisms are exothermic; however, the "outer" mechanism is more sensitive to the increase of temperature, as ΔH 11 = −8.9 kcal/mol and ΔH 12 = −19.8 kcal/mol. Clip 2 is a first unique example of the glycoluril clip, which is able to complex two resorcinol molecules, as generally, glycoluril clips interact with dihydroxyaromatics according to 1:1 stoichiometry.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of Glycoluril Molecular Clip Isomerization on the Mechanisms of Resorcinol Molecule Complexation

et al. 2020

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“…Previously, we demonstrated a convenient method of glycoluril diester clip derivative, 1 , conversion into a clip with dihydroxylated convex site, 2 (Scheme ) . The choice of glycoluril clip, 1 for building the supramolecular network resulted from its moderate ability to homodimerization along with fast monomer‐dimer exchange rate at room temperature .…”

Section: Resultsmentioning

confidence: 99%

“…Diethanolamide derivative of glycoluril clip, 2 , was prepared according the procedure previously reported . Briefly, diester derivative Glyc Clip (1.277 g; 1.616 mmol) was dissolved in anhydrous DMSO (50 ml) and 2‐ethanolamine (1.974 g; 32.3 mmol) was added.…”

Section: Methodsmentioning

confidence: 99%

“…Previously, we demonstrated a convenient method of glycoluril diester clip derivative, 1, conversion into a clip with dihydroxylated convex site, 2 (Scheme 1). [31] The choice of glycoluril clip, 1 for building the supramolecular network resulted from its moderate ability to homodimerization along with fast monomer-dimer exchange rate at room temperature. [23] We assumed that robust dynamics of clips homodimers, i. e., its association/dissociation, would facilitate the formation of supramolecular network showing both thermoresponsive and chemoresponsive properties.…”

Section: Synthesis Of Polyurethane-bearing Glycoluril Clip Motifsmentioning

confidence: 99%

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Glycoluril Clips for the Construction of Chemoresponsive Supramolecular Polymer Networks through Homodimer Cross‐Links

2019

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The formation of polymer supramolecular networks exhibiting selective sensitivity toward a narrow class of organic compounds is still a significant challenge within the area of reversibly cross‐linked materials. Glycoluril molecular clips are U‐shaped molecules, which, besides the ability to undergo self‐sorting homodimerization, exhibit selectively high molecular recognition of dihydroxyaromatic species. A glycoluril clip diol was introduced into a polymer backbone by using standard polyurethane chemistry. Immobilization of the molecular clip along the polyurethane macromolecule (Glyc Clip‐polyurethane) was shown to preserve the native association properties of the clip. Clip motifs embedded in macromolecules form homodimer cross‐links in CHCl3 and the resulting structures have a thermoresponsive character. The strength of homodimerization Khomodimer varies from 7.74 104 l mol−1 at 265 K to 9.47 102 l mol−1 at 315 K. A 30 wt % solution of Glyc Clip‐polyurethane undergoes gelation at room temperature and exhibits a constant elastic modulus, approximately 3.1 ⋅ 104 Pa, in the broad investigated frequency range. The obtained organogels exhibit selective chemoresponsive properties in the presence of resorcinol, which was demonstrated with 1H high‐resolution magic‐angle‐spinning NMR spectroscopy and rheological measurements.

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Chemoresponsive polymer systems for selective molecular recognition of organic molecules in biological systems

Gosecka

Gosecki

2020

Acta Biomaterialia

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Homodimerization driven self-assembly of glycoluril molecular clips with covalently immobilized poly(ε-caprolactone)

Cited by 8 publications

References 16 publications

Influence of Glycoluril Molecular Clip Isomerization on the Mechanisms of Resorcinol Molecule Complexation

Influence of Glycoluril Molecular Clip Isomerization on the Mechanisms of Resorcinol Molecule Complexation

Glycoluril Clips for the Construction of Chemoresponsive Supramolecular Polymer Networks through Homodimer Cross‐Links

Chemoresponsive polymer systems for selective molecular recognition of organic molecules in biological systems

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