Synthesis and Self-Assembly of Bundle-Forming α-Helical Peptide–Dendron Hybrids

Marine, Jeannette E.; Song, Shuang; Liang, Xiaoli; Rudick, Jonathan G.

doi:10.1021/acs.biomac.5b01452

Cited by 9 publications

(11 citation statements)

References 99 publications

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“…Molecular self-assembly has been widely utilized to create nanostructured soft matter for applications in biomedicine as well as in electronics and optics. [1][2][3][4][5][6] In stimulus-responsive materials, molecular ordering can give rise to novel modes of activity. For example, the photoisomerization of azobenzene (AZO) motifs is used to generate dimension changes within aligned liquid crystalline (LC) networks.…”

Section: Introductionmentioning

confidence: 99%

Photoswitchable Nanomaterials Based on Hierarchically Organized Siloxane Oligomers

Zha

Vantomme

Berrocal

et al. 2017

Adv Funct Materials

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Materials with highly ordered molecular arrangements have the capacity to display unique properties derived from their nanoscale structure. Here, the synthesis and characterization of azobenzene (AZO)-functionalized siloxane oligomers of discrete length that form photoswitchable supramolecular materials are described. Specifically, synergy between phase segregation and azobenzene crystallization leads to the self-assembly of an exfoliated 2D crystal that becomes isotropic upon photoisomerization with UV light. Consequently, the material undergoes a rapid athermal solid-to-liquid transition which can be reversed using blue light due to the unexpectedly fast 2D crystallization that is facilitated by phase segregation. In contrast, enabling telechelic supramolecular polymerization through hydrogen bonding inhibits azobenzene crystallization, and nanostructured pastes with well-ordered morphologies are obtained based on phase segregation alone, thus demonstrating block copolymer-like behavior. Therefore, by tailoring the balance of self-assembly forces in the azobenzene-functionalized siloxane oligomers, fast and reversible phase-changing materials can be engineered with various mechanical properties for applications in photolithography or switchable adhesion to lubricant properties. In these materials, contraction along the LC director occurs with isomerization of the planar trans-azobenzenes to the bent cis-azobenzenes. By limiting the depth of photoactivity, generally through utilizing the inherently high absorption coefficient of the azobenzenes, this contraction can give rise to anisotropic bending in poly mer films, [7,8] gels, [9] fibers, [10][11][12] and even crystals. [13] Different modes of motion arise with more complex molecular arrangements. For example, expansion of chiral nematic LCs along the helical axis has been utilized to create polymer coatings with photoswitchable topologies [14][15][16][17] and polymer films with macroscopic helical motion. [18] Additionally, polymer films with splay-bend configuration, in which LC-mesogens gradually change orientation throughout the film cross-section, have shown to exhibit inherently anisotropic bending as well as achieve significantly faster and larger bending when compared to uniaxially aligned films. [19][20][21] The ability of azobenzene photoisomerization to generate anisotropic dimension change and motion in LC networks typically results from increased molecular disorder caused by bent cis-azobenzene relative to networks with rod-like transazobenzene. Such photocontrol of order/disorder has been used to induce rapid nematic-to-isotropic phase transitions in LC films for applications in optical image storage [22] and holography. [23] The reversibility of azobenzene photoisomerization is beneficial for such applications, and the ability of azobenzene materials to undergo many trans-cis photoisomerization cycles without noticeable degradation in performance has been demonstrated. [24,25] Furthermore, few examples have demonstrated the photocontrolled swit...

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Section: Introductionmentioning

confidence: 99%

Photoswitchable Nanomaterials Based on Hierarchically Organized Siloxane Oligomers

Zha

Vantomme

Berrocal

et al. 2017

Adv Funct Materials

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“…The same polar and non-polar residues were used in our previously reported α-helical bundle-forming peptide-dendron hybrids. 32, 33, 54, 55 The side-chain amino group of each lysine residue is efficiently acylated using dendritic pentafluorophenyl esters. 54 DeGrado and Lear have shown that a seven-residue peptide with alternating leucine and lysine residues self-assembles into a β-sheet structure in buffered aqueous solution.…”

Section: Resultsmentioning

confidence: 99%

“…Rudimentary protein design rules offer a foundation from which to construct functional materials via programmable hierarchical organization of peptide-dendron hybrids. The recent report of self-organizable α-helix bundle-forming peptide-dendron hybrids 32, 33, 54, 55 is a promising starting point because natural helix bundles exhibit diverse functionality. 67, 68 Indeed, functional hybrid materials based on α-helix bundle-forming peptide-polymer conjugates have validated the concept of designing binding sites for light-harvesting chromophores in polymeric films.…”

Section: Resultsmentioning

confidence: 99%

“…Greater control over molecular structure can be gained by combining peptides with dendrons 20, 21 or other sequence-defined polymers. The diverse pool of α-amino acid monomers can enrich the programmable functionality of dendrons by conferring chirality, 22–24 molecular recognition, 25 surface adsorption, 26 and stimulus responsive properties 27–33 to peptide-dendron hybrids. The homogeneity of hybrids obtained from monodisperse polymers may be advantageous for applications as therapeutics.…”

Section: Introductionmentioning

confidence: 99%

“…Inspired by the tunability and processability afforded by combinations of peptides with dendrons, we have investigated hybrids of dendrons with an α-helical bundle-forming peptide. 32, 33, 54, 55 The defined arrangement of different amino acids in the core of an α-helix bundle motif could allow us to synthesize chemical gradients or unique binding sites within supramolecular dendrimers. We recently reported examples of α-helix bundle-forming peptide-dendron hybrids that self-organize in an hexagonally ordered array of columns.…”

Section: Introductionmentioning

confidence: 99%

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Peptide–dendron hybrids that adopt sequence-encoded β-sheet conformations

et al. 2018

Self Cite

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Rational design rules for programming hierarchical organization and function through mutations of monomers in sequence-defined polymers can accelerate the development of novel polymeric and supramolecular materials. Our strategy for designing peptide-dendron hybrids that adopt predictable secondary and quaternary structures in bulk is based on patterning the sites at which dendrons are conjugated to short peptides. To validate this approach, we have designed and characterized a series of β-sheet-forming peptide-dendron hybrids. Spectroscopic studies of the hybrids in films reveal that the peptide portion of the hybrids adopts the intended secondary structure.

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Helical Chirality of Supramolecular Columns and Spheres Self‐Organizes Complex Liquid Crystals, Crystals, and Quasicrystals

Percéc

Xiao

2021

Israel Journal of Chemistry

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Homochiral helical self-organizations provide some of the most fundamental architectures of biological macromolecules and of their co-assemblies although they were first discovered and elucidated only during the early 1950. Helical synthetic covalent macromolecules started to be discovered soon after and were followed by supramolecular macromolecules and their co-assemblies few decades later. This perspective will provide a brief historical development of chiral helical self-organizations in biology and in supramolecular chemistry. Helical covalent and supramolecular macromolecules self-organize and co-organize helical supramolecular columns and spherical helices that can generate complex liquid crystals, crystals including Frank-Kasper phases, and quasicrystals. The design of new functions based on synthetic helical assemblies will also be discussed. Personal events from the life of scientists contributing to these developments are also briefly mentioned.

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Synthesis and Self-Assembly of Bundle-Forming α-Helical Peptide–Dendron Hybrids

Cited by 9 publications

References 99 publications

Photoswitchable Nanomaterials Based on Hierarchically Organized Siloxane Oligomers

Photoswitchable Nanomaterials Based on Hierarchically Organized Siloxane Oligomers

Peptide–dendron hybrids that adopt sequence-encoded β-sheet conformations

Helical Chirality of Supramolecular Columns and Spheres Self‐Organizes Complex Liquid Crystals, Crystals, and Quasicrystals

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