Exploring Helical Peptides and Foldamers for the Design of Metal Helix Frameworks: Current Trends and Future Perspectives

Bajpayee, Nikhil; Vijayakanth, Thangavel; Rencus‐Lazar, Sigal; Dasgupta, Sneha; Desai, Aamod V.; Jain, Rahul; Gazit, Ehud; Misra, Rajkumar

doi:10.1002/ange.202214583

Cited by 4 publications

(2 citation statements)

References 107 publications

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“…As opposed to rigid aromatic linkers, some naturally occurring ligands such as amino acids, carboxylic acids, and their derivatives are more hydrophilic due to the presence of numerous polar functional groups, including hydroxyl, amino, and carbonyl moieties in their side chains. − These monomers are easily accessed, making them attractive for constructing COFs. However, due to the flexible conformation of the aliphatic chains, incorporating these linkers during synthesis often generates disordered and nonporous structures. − Another challenge arises from the fact that the incorporation of an aliphatic chain may disrupt the π-conjugation within the molecular framework, leading to an increased optical band gap and the loss of visible light absorption, both undesirable for a photocatalytic COF.…”

Section: Introductionmentioning

confidence: 99%

Constructing Photocatalytic Covalent Organic Frameworks with Aliphatic Linkers

Xu,

Wang,

Zhang

et al. 2024

J. Am. Chem. Soc.

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Photocatalytic covalent organic frameworks (COFs) are typically constructed with rigid aromatic linkers for crystallinity and extended π-conjugation. However, the essential hydrophobicity of the aromatic backbone can limit their performances in water-based photocatalytic reactions. Here, we for the first time report the synthesis of hydrophilic COFs with aliphatic linkers [tartaric acid dihydrazide (TAH) and butanedioic acid dihydrazide] that can function as efficient photocatalysts for H 2 O 2 and H 2 evolution. In these hydrophilic aliphatic linkers, the specific multiple hydrogen bonding networks not only enhance crystallization but also ensure an ideal compatibility of crystallinity, hydrophilicity, and light harvesting. The resulting aliphatic linker COFs adopt an unusual ABC stacking, giving rise to approximately 0.6 nm nanopores with an improved interaction with water guests. Remarkably, both aliphatic linker-based COFs show strong visible light absorption, along with a narrow optical band gap of ∼1.9 eV. The H 2 O 2 evolution rate for TAH-COF reaches up to 6003 μmol h −1 g −1 , in the absence of sacrificial agents, surpassing the performance of all previously reported COF-based photocatalysts. Theoretical calculations reveal that the TAH linker can enhance the indirect two-electron oxygen reduction reaction for H 2 O 2 production by improving the O 2 adsorption and stabilizing the *OOH intermediate. This study opens a new avenue for constructing semiconducting COFs using nonaromatic linkers.

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Section: Introductionmentioning

confidence: 99%

Constructing Photocatalytic Covalent Organic Frameworks with Aliphatic Linkers

Xu,

Wang,

Zhang

et al. 2024

J. Am. Chem. Soc.

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“…While the micro-structure of peptide-based hydrogels, and their mechanical properties, have been extensively studied, with several techniques [ 21 , 35 , 36 ], such as rheometry [ 37 , 38 , 39 ], static small-angle scattering [ 40 , 41 ], and transmission electron microscopy [ 42 , 43 ], the kinetics of aggregation and the following gelation have been investigated much less. A relatively small number of works have investigated the assembly process using circular dichroism (CD) [ 44 , 45 , 46 , 47 ], Fourier-transform infrared spectroscopy (FTIR) [ 48 ], and thioflavin T fluorescence [ 34 , 49 ]. To our knowledge, light scattering studies of the SAP self-assembly kinetics, are still lacking.…”

Section: Introductionmentioning

confidence: 99%

A Light Scattering Investigation of Enzymatic Gelation in Self-Assembling Peptides

Buzzaccaro

Ruzzi

Gelain

et al. 2023

Gels

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Self-assembling peptides (SAPs) have been increasingly studied as hydrogel–former gelators because they can create biocompatible environments. A common strategy to trigger gelation, is to use a pH variation, but most methods result in a change in pH that is too rapid, leading to gels with hardly reproducible properties. Here, we use the urea–urease reaction to tune gel properties, by a slow and uniform pH increase. We were able to produce very homogeneous and transparent gels at several SAP concentrations, ranging from c=1g/L to c=10g/L. In addition, by exploiting such a pH control strategy, and combining photon correlation imaging with dynamic light scattering measurements, we managed to unravel the mechanism by which gelation occurs in solutions of (LDLK)3-based SAPs. We found that, in diluted and concentrated solutions, gelation follows different pathways. This leads to gels with different microscopic dynamics and capability of trapping nanoparticles. At high concentrations, a strong gel is formed, made of relatively thick and rigid branches that firmly entrap nanoparticles. By contrast, the gel formed in dilute conditions is weaker, characterized by entanglements and crosslinks of very thin and flexible filaments. The gel is still able to entrap nanoparticles, but their motion is not completely arrested. These different gel morphologies can potentially be exploited for controlled multiple drug release.

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Biasing the Formation of Solution‐Unstable Intermediates in Coordination Self‐Assembly by Mechanochemistry

Liu,

et al. 2023

Chemistry A European J

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Due to the reversible nature of coordination bonds and solvation effect, coordination self‐assembly pathways are often difficult to elucidate experimentally in solution, as intermediates and products are in constant equilibration. Herein, we showed that some of these transient and high‐energy self‐assembly intermediates can be accessed by means of ball‐milling approaches. Among them, highly aqueous‐unstable Pd3L11 and Pd6L14 open‐cage intermediates of the framed Fujita Pd6L14 cage and Pd2L22, Pd3L21 and Pd4L22 intermediates of Mukherjee Pd6L24 capsule are successfully trapped in solid‐state, where L1 = 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine and L2 = 1,3,5‐tris(1‐imidazolyl)benzene). Their structures are assigned by a combination of solution‐based characterization tools such as standard NMR spectroscopy, DOSY NMR, ESI‐MS and X‐ray diffraction. Collectively, our result highlights the opportunity of using mechanochemistry to access unique chemical space with vastly different reactivity compared to conventional solution‐based supramolecular self‐assembly reactions.

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Exploring Helical Peptides and Foldamers for the Design of Metal Helix Frameworks: Current Trends and Future Perspectives

Cited by 4 publications

References 107 publications

Constructing Photocatalytic Covalent Organic Frameworks with Aliphatic Linkers

Constructing Photocatalytic Covalent Organic Frameworks with Aliphatic Linkers

A Light Scattering Investigation of Enzymatic Gelation in Self-Assembling Peptides

Biasing the Formation of Solution‐Unstable Intermediates in Coordination Self‐Assembly by Mechanochemistry

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