Vesicles and Organogels from Foldamers: A Solvent-Modulated Self-Assembling Process

Cai, Wei; Wang, Gui-Tao; Xu, Yun‐Xiang; Jiang, Xiumin; Li, Zhan‐Ting

doi:10.1021/ja801618p

Cited by 163 publications

(97 citation statements)

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“…16 The TEM image of the vesicles evidenced their hollow feature, because the global structures exhibited discernible rings around the periphery, which should be produced through the evaporation of the entrapped solvent on the surface (Figure 1c). 9 These results indicate that the six DOAOE groups in 1 were efficient in promoting the stacking of its central aromatic backbone to form ordered membranes.…”

Section: Resultsmentioning

confidence: 89%

“…Previously, we have established that the cooperative interactions of the stacking of the central aromatic units, the intermolecular hydrogen bonding of the amide units of the side chain and the hydrophobic interaction of the appended octyl chains induce the formation of vesicles for other molecules. 9,10 The formation of the vesicles by compound 1 should follow the similar mechanism. That is, the one-layer stacking of the molecule forms column-styled architectures, which further aggregate to generate one-layered membrane.…”

Section: Resultsmentioning

confidence: 94%

“…[1][2][3][4][5] We recently reported that hydrogen bonding-induced aromatic hydrazide foldamers form vesicles in methanol or its aqueous solution, [6][7][8] which are driven by the stacking of the rigid backbone and the hydrogen bonding and van der Waals interactions of the appended aliphatic amide chain, i.e., 2-(2-(dioctylamino)-2-oxoethyl-amino)-2-oxoethoxyl unit (DOAOE). 9,10 Control experiments showed that this new amphiphilic chain is more robust than the conventionally used hydrophilic oligoglycol groups in inducing the formation of vesicles in polar media. To further test if DOAOE is efficient for other kinds of aromatic compounds, we have synthesized aromatic heterocycle 1, which bears six DOAOE groups.…”

Section: Introductionmentioning

confidence: 99%

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Self‐Assembly of Vesicles by a 2,6‐Di(7‐benzamidy)quinolin‐2‐ yl)pyridine Derivative Tuned by an Amphiphilic Amide Chain

You

Zhao

2010

Chin. J. Chem.

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This paper describes 2-(2-(dioctylamino)-2-oxoethyl-amino)-2-oxoethoxyl (DOAOE)-tuned self-assembly of vesicles from a 2,6-di(7-benzamidy)-quinolin-2-yl)pyridine derivative. Scanning electron (SEM), transmission electron (TEM) and optical microscopy and dynamic light scattering (DLS) studies reveal that the molecule self-assembles into vesicular structures in methanol. The influence of the transition metal ions and trifluoroacetic acid on the formation of the vesicles was investigated. The results illustrate that DOAOE is robust in promoting the formation of vesicles for aromatic systems in polar medium.

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Self‐Assembly of Vesicles by a 2,6‐Di(7‐benzamidy)quinolin‐2‐ yl)pyridine Derivative Tuned by an Amphiphilic Amide Chain

You

Zhao

2010

Chin. J. Chem.

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“…例如, 这类结构可以形成不同内径的环形构象, 作为合成的非环主体分子选择性的络合中性或离子型客体 [13～15] . 由于其芳酰胺骨架具有结构预组织特征, 它们也可以在极性或非极性溶剂中堆积形成凝胶和囊泡等三维组装体 [16,17] . 这类折叠结构还可以作为预组织骨架, 用于设计不同的超分子砌块 [17～20] , 促进大环结构的形成 [21～28] , 控制大分子力学性质和轮烷分子梭的穿梭速率等 [29～31] .…”

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Evaluation on the Stability of the Intramolecular N—H…OMe Hydrogen Bonds of Aromatic Amide Foldamers

施朱明¹,

宋宇²,

陆方³

et al. 2013

Acta Chim. Sinica

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To evaluate the relative stability of different intramolecular N-H…OMe hydrogen bonds of aromatic amide-based foldamers, 3-, 5-, and 7-mer aromatic amide foldamers F-3, F-5 and F-7, which possess one, two, and three different amide units, have been constructed from benzene-1,3-diamine and isophthalic acid derivatives.1 H NMR experiments in CDCl 2 CDCl 2 and DMSO-d 6 showed that the hydrogen bonds formed in the central area of the foldamer backbones are least stable, whereas the hydrogen bonds formed at the two ends are most stable.1 H NMR hydrogen-deuterium exchange experiments for F-3, F-5 and F-7 in CDCl 2 CDCl 2 -CD 3 OD (19∶1, V/V) and DMSO-d 6 -CD 3 OD (19∶1, V/V) were performed. In the former less polar solvent mixture, the half-life values of the process, corresponding to amides from the central area to the end areas, were determined to be 140 h for F-3, 71.8 and 405 h for F-5, and 36.3, 216 and 314 h for F-7, respectively. In the latter more polar solvent mixture, the related values were evaluated to be 97.1 h for F-3, 69.0 and 300 h for F-5, and 13.5, 38.3 and 57.5 h for F-7, respectively. These quantitative results are consistent with the above 1 H NMR observation. To further assess the strength of the intramolecular hydrogen bonds, the three folded aromatic amide segments have also been incorporated into the main chains of dodecane-1,12-diamine-derived amide polymers to afford macromolecules P-3, P-5 and P-7. The degree of polymerization of the macromolecules was determined by GPC to be 22, 14 and 13, respectively. Force-extension curves obtained from single molecular force spectroscopy (SMFS) revealed that, in tetrachloroethane, all the three macromolecules exhibited saw-tooth force peaks, which had been attributed to the step-by-step breaking of the intramolecular hydrogen bonds of the foldamer segments. P-3 exhibited 4 peaks at ca. 83, 121, 181 and 236 pN, P-5 displayed 7 peaks at ca. 20,44, 73, 101, 130, 171 and 278 pN, and P-7 generated 8 peaks at ca. 31, 43, 50, 60, 90, 152, 173 and 221 pN. The increasing number of the force peaks observed from P-3 to P-5 and P-7 was ascribed to the increasing number of the intramolecular hydrogen bonds. It was proposed that the peaks at lower forces corresponded to the less stable hydrogen bonds, whereas those observed at higher forces were produced by the breaking of the more stable ones. The fact that the first peaks of P-3 was higher than that of P-5 and P-7 indicated that the intramolecular hydrogen bonds of P-3 were pronouncedly more stable than some of the intramolecular hydrogen bonds of P-5 and P-7, which is consistent with the above 1 H NMR and hydrogen-deuterium exchange observations. Similar results were also observed for P-5 and P-7 in hexadecane, whereas P-3 did not generate measurable force peaks possibly due to the strong absorption of its short, but more planar foldamer segments to the surface of the slide. Simulated stretching curves of the three macromolecules were also consistent with the SMFS results.

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“…Over the past decade, dramatically increased attention has been focused on the organogels [4], due to their widespread potential applications in sensors [5], photonics [6], electronic devices, regenerative medicine [7], catalysis [8], cosmetics and many other fields [2][3][4]. A number of compounds with diverse structures have been developed as LMOGs, including steroids [9,10], triterpenoids [11,12], amino acids [13][14][15], hydrazide [16][17][18][19][20], urea derivatives [21][22][23], and π-systems and chromophores [24][25][26][27]. In particular, many LMOGs have been developed as smart gel systems that are responsive to stimuli, such as ions [28,29], molecules [30,31], pH [32,33], redox [34,35], light [36,37], electric field [38], and ultrasound [39,40].…”

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confidence: 99%

Amidourea-based homoduplex as a super organogelator

Chu

Chen

2012

Chin. Sci. Bull.

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The amidourea-based homoduplex was developed as a super organogelator, which could form stable gels in wide-tested solvents. And the reversible gel to solution transition was responsive to heat/cool and acid/base stimuli. The organogels were extensively investigated by 1 H NMR, UV-visible absorption spectroscopy, fluorescence spectroscopy, scanning electron microscopy, transmission electron microscopy and powder X-ray diffraction. Based on these data, the gelation mechanism was rationally proposed. The hydrogen-bonded homoduplexes served as the basic assembling units, and further aggregated into three dimensional networks via - stacking and van der Waals interactions, which consequently led to the entangled fibers for the gel formation. amidourea, homoduplex, organogelator, gelation mechanism Citation:Chu W J, Chen C F. Amidourea-based homoduplex as a super organogelator. Chin Sci Bull, 2012Bull, , 57: 42784283, doi: 10.1007 Gels are well-known soft materials with daily applications, such as hair gel, contact lenses, gelatin desserts, lithium grease and so on. Among them, one of the most emerging categories is organogels, which are composed of a selfassembled supramolecular structure of low-molecular-mass organic gelators (LMOGs) and a large volume of organic liquids immobilized therein [1][2][3] Generally, organogels are formed by LMOGs selfassembling into reticular three-dimensional networks with solvent molecules entrapped inside through non-covalent interactions. However, the gelation mechanism on the molecular level is elusive, and a rational correlation of molecular structure and gelation ability in a given solvent still remains a challenge. The development of new LMOG with a well-understood gelation mechanism will provide valuable insights into the gelation process, and thus may promote the rational design of organogelators. Recently, hydrogen-bonded molecular duplexes based on the hydrazide [18] and amide [41] units are reported as LMOGs, but both of them gelate only in several apolar solvents. As a continuation of our previous work on the amidourea-based hydrogen-bonded molecular duplexes [42], we herein report the amidourea-based homoduplex ( Figure 1) as a super LMOG, which form stable gels in wide-tested solvents. And the reversible gel to solution transition is responsive to heat/cool and acid/base stimuli. Moreover, we investigated the organogels of 1 via 1 H NMR, UV-visible absorption spectroscopy, fluorescence spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD), and attempted to explore the gelation mechanism.

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Vesicles and Organogels from Foldamers: A Solvent-Modulated Self-Assembling Process

Cited by 163 publications

References 36 publications

Self‐Assembly of Vesicles by a 2,6‐Di(7‐benzamidy)quinolin‐2‐ yl)pyridine Derivative Tuned by an Amphiphilic Amide Chain

Self‐Assembly of Vesicles by a 2,6‐Di(7‐benzamidy)quinolin‐2‐ yl)pyridine Derivative Tuned by an Amphiphilic Amide Chain

Evaluation on the Stability of the Intramolecular N—H…OMe Hydrogen Bonds of Aromatic Amide Foldamers

Amidourea-based homoduplex as a super organogelator

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