Abstract:We demonstrate an in situ ultrasonic approach to influence self-assembly across the supramolecular to micron length scales, showing enhancement of supramolecular interactions, chirality and orientation, which depends on the peptide sequence and solvent environment. This is the first successful demonstration of using oscillating pressure waves to generate anisotropic organo- and hydrogels consisting of oriented tripeptides structures.
“…These noncovalent interactions can provide highly organized molecular architectures that display reversible, instant, and visual changes in response to external stimuli, such as ultrasound, shearing stress, light, heating, magnetism, ions, pH, chiral compounds, enzymes, and gases. Typically, supramolecular gels are formed by heating a low‐molecular‐weight (LMW) gelator in an appropriate solvent at a specific concentration, then cooling . The transcription of intrinsic molecular features from the molecular level to complex supramolecular structures is realized in the sol‐to‐gel transition process.…”
Section: Introductionmentioning
confidence: 99%
“…Typically,s upramolecular gels are formed by heatingalow-molecular-weight (LMW) gelator in an appropriate solvent at as pecific concentration, then cooling. [26][27][28][29] The transcription of intrinsic molecular features from the molecularl evel to complex supramolecular structures is realized in the sol-to-gel transition process. However,n ot all self-assemblies of LMW molecules result in gelation.…”
A series of bicholesteryl-based gelators with different central linker atoms C, N, and O (abbreviated to GC, GN, and GO, respectively) have been designed and synthesized. The self-assembly processes of these gelators were investigated by using gelation tests, field-emission scanning electron microscopy, field-emission transmission electron microscopy, UV/Vis absorption, IR spectroscopy, X-ray diffraction, rheology, and contact-angle experiments. The gelation ability, self-assembly morphology, rheological, and surface-wettability properties of these gelators strongly depend on the central linker atom of the gelator molecule. Specifically, GC and GN can form gels in three different solvents, whereas GO can only form a gel in N,N-dimethylformamide (DMF). Morphologies from nanofibers and nanosheets to nanospheres and nanotubes can be obtained with different central atoms. Gels of GC, GN, and GO formed in the same solvent (DMF) have different tolerances to external forces. All xerogels gave a hydrophobic surface with contact angles that ranged from 121 to 152°. Quantum-chemical calculations indicate that the GC, GN, and GO molecules have very different steric structures. The results demonstrate that the central linker atom can efficiently modulate the molecular steric structure and thus regulate the supramolecular self-assembly process and properties of gelators.
“…These noncovalent interactions can provide highly organized molecular architectures that display reversible, instant, and visual changes in response to external stimuli, such as ultrasound, shearing stress, light, heating, magnetism, ions, pH, chiral compounds, enzymes, and gases. Typically, supramolecular gels are formed by heating a low‐molecular‐weight (LMW) gelator in an appropriate solvent at a specific concentration, then cooling . The transcription of intrinsic molecular features from the molecular level to complex supramolecular structures is realized in the sol‐to‐gel transition process.…”
Section: Introductionmentioning
confidence: 99%
“…Typically,s upramolecular gels are formed by heatingalow-molecular-weight (LMW) gelator in an appropriate solvent at as pecific concentration, then cooling. [26][27][28][29] The transcription of intrinsic molecular features from the molecularl evel to complex supramolecular structures is realized in the sol-to-gel transition process. However,n ot all self-assemblies of LMW molecules result in gelation.…”
A series of bicholesteryl-based gelators with different central linker atoms C, N, and O (abbreviated to GC, GN, and GO, respectively) have been designed and synthesized. The self-assembly processes of these gelators were investigated by using gelation tests, field-emission scanning electron microscopy, field-emission transmission electron microscopy, UV/Vis absorption, IR spectroscopy, X-ray diffraction, rheology, and contact-angle experiments. The gelation ability, self-assembly morphology, rheological, and surface-wettability properties of these gelators strongly depend on the central linker atom of the gelator molecule. Specifically, GC and GN can form gels in three different solvents, whereas GO can only form a gel in N,N-dimethylformamide (DMF). Morphologies from nanofibers and nanosheets to nanospheres and nanotubes can be obtained with different central atoms. Gels of GC, GN, and GO formed in the same solvent (DMF) have different tolerances to external forces. All xerogels gave a hydrophobic surface with contact angles that ranged from 121 to 152°. Quantum-chemical calculations indicate that the GC, GN, and GO molecules have very different steric structures. The results demonstrate that the central linker atom can efficiently modulate the molecular steric structure and thus regulate the supramolecular self-assembly process and properties of gelators.
“…Pappas et al demonstrated that short, curved nanofibres of the tripeptides D FFD and D FFI can be converted to bundles of parallel nanofibres through directional sonication, resulting in strong gels with pronounced supramolecular chirality. 434 342 More strikingly, the azobenzene derivative 43 produces a strong sound-induced LD signal in cyclohexane solutions of its trans form but becomes LD silent when isomerised, due to fragmentation of the fibrous aggregates into non-orientable spheroidal particles (Fig. 46).…”
. (2016) 'Gels with sense : supramolecular materials that respond to heat, light and sound.', Chemical society reviews., 45 (23). pp. 6546-6596. Further information on publisher's website:https://doi.org/10.1039/C6CS00435KPublisher's copyright statement:Additional information:
Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Advances in the field of supramolecular chemistry have made it possible, in many situations, to reliably engineer soft materials to address a specific technological problem. Particularly exciting are "smart" gels that undergo reversible physical changes on exposure to remote, non-invasive environmental stimuli. This review explores the development of gels which are transformed by heat, light and ultrasound, as well as other mechanical inputs, applied voltages and magnetic fields. Focusing on small-molecule gelators, but with reference to organic polymers and metal-organic systems, we examine how the structures of gelator assemblies influence the physical and chemical mechanisms leading to thermo-, photo-and mechano-switchable behaviour. In addition, we evaluate how the unique and versatile properties of smart materials may be exploited in a wide range of applications, including catalysis, crystal growth, ion sensing, drug delivery, data storage and biomaterial replacement.
“…Manipulating system temperature or pH can promote hierarchical order among synthetic nanofibers by balancing intermolecular forces [9][10][11] . Likewise, shear flow, magnetic field, and ultrasound can be applied to induce peptide nanofiber alignment [12][13][14][15] . Alternatively, amino acid sequences can be tailored to promote nanofiber lateral association 16,17 , although these examples have been limited to electrostatic and aromatic-aromatic interactions involving the few natural charged or hydrophobic amino acids, respectively.…”
Glycosylation alters protein form and function by establishing intermolecular forces that mediate specific interactions while preventing non-specific aggregation. Self-assembled peptide nanofibers modified with carbohydrates are increasingly used as biomaterials to mimic glycosylated protein function, yet the influence of carbohydrate conjugates on nanofiber structure remains poorly defined. Here we show that a dense carbohydrate surface layer can facilitate hierarchical organization of peptide nanofibers into anisotropic networks. Glycosylated peptide nanofibers remain dispersed in dilute conditions, whereas non-glycosylated nanofibers tend to aggregate. In crowded conditions, some glycosylated nanofibers laterally associate and align. This behavior depends on carbohydrate chemistry, particularly hydroxyls, suggesting involvement of short-range attractive forces. Macroscopic gels fabricated from densely glycosylated peptide nanofibers are resistant to non-specific interactions with proteins, mammalian cells, and bacteria, yet selectively bind lectins, analogous to natural lowfouling mucosal barriers. Collectively, these observations demonstrate that glycosylation can inform structure in addition to endowing function to peptide-based supramolecular biomaterials.
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