Rational Design of Multiple-Stimulus-Responsive Materials via Supramolecular Self-Assembly

Peptide and low molecular weight amino acid-based materials that self-assemble in response to environmental triggers are highly desirable candidates in forming functional materials with tunable biophysical properties. In this paper, we explore redox-sensitive self-assembly of cationic phenylalanine derivatives conjugated to naphthalene diimide (NDI). Self-assembly of the cationic Phe-NDI conjugates into nanofibrils was induced in aqueous solvent at high ionic strength. Under reducing conditions, these self-assembled Phe-NDI conjugate fibrils underwent a morphological change to non-fibril aggregates. Upon reoxidation, the initially observed fibrils were reformed. The study herein provides an interesting strategy to effect reversible switching of the structure of supramolecular materials that can be applied to the development of sophisticated stimulus-responsive materials.

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Carbocycle-Based Organogelators: Influence of Chirality and Structural Features on Their Supramolecular Arrangements and Properties

Gels ◽

10.3390/gels7020054 ◽

2021 ◽

Vol 7 (2) ◽

pp. 54

Author(s):

Rosa M. Ortuño

Keyword(s):

Smart Materials ◽

Self Assembly ◽

Rational Design ◽

Structural Features ◽

Stimuli Responsive ◽

Polycyclic Compounds ◽

Relative Configuration ◽

Responsive Materials ◽

Self Assembling ◽

Donor Acceptor

The rational design and engineer of organogel-based smart materials and stimuli-responsive materials with tuned properties requires the control of the non-covalent forces driving the hierarchical self-assembly. Chirality, as well as cis/trans relative configuration, also plays a crucial role promoting the morphology and characteristics of the aggregates. Cycloalkane derivatives can provide chiral chemical platforms allowing the incorporation of functional groups and hydrophobic structural units able for a convenient molecular stacking leading to gels. Restriction of the conformational freedom imposed by the ring strain is also a contributing issue that can be modulated by the inclusion of flexible segments. In addition, donor/acceptor moieties can also be incorporated favoring the interactions with light or with charged species. This review offers a perspective on the abilities and properties of carbocycle-based organogelators starting from simple cycloalkane derivatives, which were the key to establish the basis for an effective self-assembling, to sophisticated polycyclic compounds with manifold properties and applications.

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Synergetic integration of computer-aided design, experimental synthesis, and self-assembly for the rational design of peptide/protein nanofibrils

Artificial Protein and Peptide Nanofibers ◽

10.1016/b978-0-08-102850-6.00010-3 ◽

2020 ◽

pp. 219-239

Author(s):

Ke Zheng ◽

Jing Ren ◽

Yawen Liu ◽

Shengjie Ling

Keyword(s):

Self Assembly ◽

Computer Aided Design ◽

Rational Design ◽

Computer Aided ◽

Aided Design

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Self-Assembly, Symmetry, and Molecular Architecture: Coordination as the Motif in the Rational Design of Supramolecular Metallacyclic Polygons and Polyhedra

Accounts of Chemical Research ◽

10.1021/ar9602011 ◽

1997 ◽

Vol 30 (12) ◽

pp. 502-518 ◽

Cited By ~ 906

Author(s):

Peter J. Stang ◽

Bogdan Olenyuk

Keyword(s):

Self Assembly ◽

Rational Design ◽

Molecular Architecture

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Examining the structure of the mature amyloid fibril

Biochemical Society Transactions ◽

10.1042/bst0300521 ◽

2002 ◽

Vol 30 (4) ◽

pp. 521-525 ◽

Cited By ~ 43

Author(s):

O. S. Makin ◽

L. C. Serpell

Keyword(s):

Self Assembly ◽

Rational Design ◽

Amyloid Fibrils ◽

Structural Information ◽

X Ray ◽

X Ray Crystallography ◽

Cryo Electron Microscopy ◽

Fibre Diffraction ◽

Complementary Techniques ◽

Mature Fibril

The pathogenesis of the group of diseases known collectively as the amyloidoses is characterized by the deposition of insoluble amyloid fibrils. These are straight, unbranching structures about 70–120 å (1 å = 0.1 nm) in diameter and of indeterminate length formed by the self-assembly of a diverse group of normally soluble proteins. Knowledge of the structure of these fibrils is necessary for the understanding of their abnormal assembly and deposition, possibly leading to the rational design of therapeutic agents for their prevention or disaggregation. Structural elucidation is impeded by fibril insolubility and inability to crystallize, thus preventing the use of X-ray crystallography and solution NMR. CD, Fourier-transform infrared spectroscopy and light scattering have been used in the study of the mechanism of fibril formation. This review concentrates on the structural information about the final, mature fibril and in particular the complementary techniques of cryo-electron microscopy, solid-state NMR and X-ray fibre diffraction.

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Ag–Au Core–Shell Triangular Nanoprisms for Improving p-g-C3N4 Photocatalytic Hydrogen Production

Nanomaterials ◽

10.3390/nano11123347 ◽

2021 ◽

Vol 11 (12) ◽

pp. 3347

Author(s):

Yali Guo ◽

Anzhou Xu ◽

Juan Hou ◽

Qingcui Liu ◽

Hailong Li ◽

...

Keyword(s):

Hydrogen Production ◽

Self Assembly ◽

Rational Design ◽

Photogenerated Electron ◽

Core Shell ◽

Co Catalyst ◽

Replacement Method ◽

Assembly Method ◽

Free Replacement ◽

Electron Holes

Ag–Au core–shell triangular nanoprisms (Ag@Au TNPs) have aroused extensive research interest in the field of hydrogen evolution reaction (HER) due to their strong plasmon effect and stability. Here, Ag@Au TNPs were fabricated by the galvanic-free replacement method. Then, we loaded them on protonated g-C3N4 nanoprisms (P–CN) by the electrostatic self-assembly method as an efficient plasmonic photocatalyst for HER. The hydrogen production rate of Ag@Au TNPs/P–CN (4.52 mmol/g/h) is 4.1 times higher than that of P–CN (1.11 mmol/g/h) under simulated sunlight irradiation, making it the most competitive material for water splitting. The formed Schottky junction helps to trap the hot electrons generated from Ag@Au TNPs, and the well-preserved tips of the Ag@Au TNPs can effectively generate an electromagnetic field to inhibit the photogenerated electron–holes pairs recombination. This study suggests that the rational design of Ag@Au TNPs by the galvanic-free replacement method is an effective co-catalyst for HER and boosting the additional combination of plasmonic metals and catalyst metals for the enhancement to HER.

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Multiphoton Laser Fabrication of Hybrid Photo-Activable Biomaterials

Sensors ◽

10.3390/s21175891 ◽

2021 ◽

Vol 21 (17) ◽

pp. 5891

Author(s):

Margaux Bouzin ◽

Amirbahador Zeynali ◽

Mario Marini ◽

Laura Sironi ◽

Riccardo Scodellaro ◽

...

Keyword(s):

Mechanical Characteristics ◽

Direct Writing ◽

Laser Direct Writing ◽

Responsive Materials ◽

Polymeric Blends ◽

Sensing Platforms ◽

Stimulus Responsive ◽

Essential Parameter ◽

Increasing Demand ◽

And Personalized Medicine

The possibility to shape stimulus-responsive optical polymers, especially hydrogels, by means of laser 3D printing and ablation is fostering a new concept of “smart” micro-devices that can be used for imaging, thermal stimulation, energy transducing and sensing. The composition of these polymeric blends is an essential parameter to tune their properties as actuators and/or sensing platforms and to determine the elasto-mechanical characteristics of the printed hydrogel. In light of the increasing demand for micro-devices for nanomedicine and personalized medicine, interest is growing in the combination of composite and hybrid photo-responsive materials and digital micro-/nano-manufacturing. Existing works have exploited multiphoton laser photo-polymerization to obtain fine 3D microstructures in hydrogels in an additive manufacturing approach or exploited laser ablation of preformed hydrogels to carve 3D cavities. Less often, the two approaches have been combined and active nanomaterials have been embedded in the microstructures. The aim of this review is to give a short overview of the most recent and prominent results in the field of multiphoton laser direct writing of biocompatible hydrogels that embed active nanomaterials not interfering with the writing process and endowing the biocompatible microstructures with physically or chemically activable features such as photothermal activity, chemical swelling and chemical sensing.

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Chapter 12. Responsive Materials by the Self-assembly of Low Molecular Weight Gelators

Smart Materials Series - Chemoresponsive Materials ◽

10.1039/9781782622420-00332 ◽

2015 ◽

pp. 332-363 ◽

Cited By ~ 1

Author(s):

Emily R. Draper ◽

Dave J. Adams

Keyword(s):

Molecular Weight ◽

Self Assembly ◽

The Self ◽

Low Molecular Weight ◽

Responsive Materials ◽

Low Molecular Weight Gelators

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pH- and concentration-dependent supramolecular self-assembly of a naturally occurring octapeptide

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.16.168 ◽

2020 ◽

Vol 16 ◽

pp. 2017-2025

Author(s):

Goutam Ghosh ◽

Gustavo Fernández

Keyword(s):

Self Assembly ◽

Ph Value ◽

Secondary Structures ◽

Random Coil ◽

Conformational Transformation ◽

Stimuli Responsive ◽

Responsive Materials ◽

Force Microscopy ◽

Assembly Behavior ◽

Novel Drug

Peptide-based biopolymers represent highly promising biocompatible materials with multiple applications, such as tailored drug delivery, tissue engineering and regeneration, and as stimuli-responsive materials. Herein, we report the pH- and concentration-dependent self-assembly and conformational transformation of the newly synthesized octapeptide PEP-1. At pH 7.4, PEP-1 forms β-sheet-rich secondary structures into fractal-like morphologies, as verified by circular dichroism (CD), Fourier-transform infrared (FTIR) spectroscopy, thioflavin T (ThT) fluorescence spectroscopy assay, and atomic force microscopy (AFM). Upon changing the pH value (using pH 5.5 and 13.0), PEP-1 forms different types of secondary structures and resulting morphologies due to electrostatic repulsion between charged amino acids. PEP-1 can also form helical or random-coil secondary structures at a relatively low concentration. The obtained pH-sensitive self-assembly behavior of the target octapeptide is expected to contribute to the development of novel drug nanocarrier assemblies.

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