Responsive hybrid (poly)peptide–polymer conjugates

Naphthalene-diimide (NDI) derived building blocks have been explored extensively for supramolecular assembly as they exhibit attractive photophysical properties, suitable for applications in organic optoelectronics. Core-substituted derivatives of the NDI chromophore (cNDI) differ significantly from the parent NDI dye in terms of optical and redox properties. Adequate molecular engineering opportunities and substitution-dependent tunable optoelectronic properties make cNDI derivatives highly promising candidates for supramolecular assembly and functional material. This short review discusses recent development in the area of functional supramolecular assemblies based on cNDIs and related molecules.

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Amyloid fibril-directed synthesis of silica core–shell nanofilaments, gels, and aerogels

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1819640116 ◽

2019 ◽

Vol 116 (10) ◽

pp. 4012-4017 ◽

Cited By ~ 20

Author(s):

Yiping Cao ◽

Sreenath Bolisetty ◽

Gianna Wolfisberg ◽

Jozef Adamcik ◽

Raffaele Mezzenga

Keyword(s):

Amyloid Fibril ◽

Functional Materials ◽

Building Blocks ◽

Inorganic Materials ◽

Core Shell ◽

Shear Stresses ◽

Bending Rigidity ◽

Widespread Application ◽

Nonmonotonic Dependence ◽

Silica Core

Amyloid fibrils have evolved from purely pathological materials implicated in neurodegenerative diseases to efficient templates for last-generation functional materials and nanotechnologies. Due to their high intrinsic stiffness and extreme aspect ratio, amyloid fibril hydrogels can serve as ideal building blocks for material design and synthesis. Yet, in these gels, stiffness is generally not paired by toughness, and their fragile nature hinders significantly their widespread application. Here we introduce an amyloid-assisted biosilicification process, which leads to the formation of silicified nanofibrils (fibril–silica core–shell nanofilaments) with stiffness up to and beyond ∼20 GPa, approaching the Young’s moduli of many metal alloys and inorganic materials. The silica shell endows the silicified fibrils with large bending rigidity, reflected in hydrogels with elasticity three orders of magnitude beyond conventional amyloid fibril hydrogels. A constitutive theoretical model is proposed that, despite its simplicity, quantitatively interprets the nonmonotonic dependence of the gel elasticity upon the filaments bundling promoted by shear stresses. The application of these hybrid silica–amyloid hydrogels is demonstrated on the fabrication of mechanically stable aerogels generated via sequential solvent exchange, supercriticalCO2removal, and calcination of the amyloid core, leading to aerogels of specific surface area as high as 993m2/g, among the highest values ever reported for aerogels. We finally show that the scope of amyloid hydrogels can be expanded considerably by generating double networks of amyloid and hydrophilic polymers, which combine excellent stiffness and toughness beyond those of each of the constitutive individual networks.

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A Dynamic Route to Structure and Function: Recent Advances in Imine-Based Organic Nanostructured Materials

Australian Journal of Chemistry ◽

10.1071/ch12349 ◽

2013 ◽

Vol 66 (1) ◽

pp. 9 ◽

Cited By ~ 26

Author(s):

Yi Liu ◽

Zhan-Ting Li

Keyword(s):

Self Assembly ◽

Reaction System ◽

Functional Materials ◽

Building Blocks ◽

The Self ◽

Interlocked Molecules ◽

Functional Aspects ◽

Imine Bond ◽

And Function ◽

Dynamic Route

The chemistry of imine bond formation from simple aldehyde and amine precursors is among the most powerful dynamic covalent chemistries employed for the construction of discrete molecular objects and extended molecular frameworks. The reversible nature of the C=N bond confers error-checking and proof-reading capabilities in the self-assembly process within a multi-component reaction system. This review highlights recent progress in the self-assembly of complex organic molecular architectures that are enabled by dynamic imine chemistry, including molecular containers with defined geometry and size, mechanically interlocked molecules, and extended frameworks and polymers, from building blocks with preprogrammed steric and electronic information. The functional aspects associated with the nanometer-scale features not only place these dynamically constructed nanostructures at the frontier of materials sciences, but also bring unprecedented opportunities for the discovery of new functional materials.

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Straightforward Preparation of Supramolecular Janus Nanorods by Hydrogen Bonding of End-Functionalized Polymers

10.26434/chemrxiv.12206384.v1 ◽

2020 ◽

Author(s):

Shuaiyuan Han ◽

Sandrine Pensec ◽

Cédric Lorthioir ◽

Jacques Jestin ◽

Jean-Michel Guigner ◽

...

Keyword(s):

Hydrogen Bonding ◽

Self Assembly ◽

Functional Materials ◽

Phase Segregation ◽

Building Blocks ◽

Functionalized Polymers ◽

Nanometer Range ◽

One Dimensional ◽

Oil In Water ◽

First Time

Janus cylinders are one-dimensional colloids that have two faces with different compositions and functionalities and are useful as building blocks for advanced functional materials. Such anisotropic objects are difficult to prepare with nanometric dimensions. Here we describe a robust and versatile strategy to form micrometer long Janus nanorods with diameters in the 10-nanometer range, by self-assembly in water of end-functionalized polymers. For the first time, the Janus topology is not a result of the phase segregation of incompatible polymer arms, but is driven by the interactions between unsymmetrical and complementary hydrogen bonded stickers. It is therefore independent of the actual polymers used and works even for compatible polymers. To illustrate their applicative potential, we show that these Janus nanorods can efficiently stabilize oil-in-water emulsions.

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Emulsion templated advanced functional materials from emerging nano building blocks

Journal of Materials Chemistry A ◽

10.1039/d1ta05420a ◽

2021 ◽

Author(s):

Chenfei Yao ◽

Ge Shi ◽

Yijie Hu ◽

Hao Zhuo ◽

Zehong Chen ◽

...

Keyword(s):

Transition Metal ◽

Functional Materials ◽

Building Blocks ◽

Metal Carbides ◽

Transition Metal Carbides ◽

The Past ◽

Great Progress

The development of emulsion templated functional materials has achieved great progress in the past decades in academic and industrial fields. Recently, new building blocks such as graphene, transition metal carbides...

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Diverse protein assembly driven by metal and chelating amino acids with selectivity and tunability

Nature Communications ◽

10.1038/s41467-019-13491-w ◽

2019 ◽

Vol 10 (1) ◽

Cited By ~ 10

Author(s):

Minwoo Yang ◽

Woon Ju Song

Keyword(s):

Amino Acids ◽

Self Assembly ◽

Protein Structures ◽

Functional Materials ◽

Building Blocks ◽

Unnatural Amino Acid ◽

Metal Coordination ◽

Specific Chemical ◽

Natural Building ◽

Kinetics Of

AbstractProteins are versatile natural building blocks with highly complex and multifunctional architectures, and self-assembled protein structures have been created by the introduction of covalent, noncovalent, or metal-coordination bonding. Here, we report the robust, selective, and reversible metal coordination properties of unnatural chelating amino acids as the sufficient and dominant driving force for diverse protein self-assembly. Bipyridine-alanine is genetically incorporated into a D3 homohexamer. Depending on the position of the unnatural amino acid, 1-directional, crystalline and noncrystalline 2-directional, combinatory, and hierarchical architectures are effectively created upon the addition of metal ions. The length and shape of the structures is tunable by altering conditions related to thermodynamics and kinetics of metal-coordination and subsequent reactions. The crystalline 1-directional and 2-directional biomaterials retain their native enzymatic activities with increased thermal stability, suggesting that introducing chelating ligands provides a specific chemical basis to synthesize diverse protein-based functional materials while retaining their native structures and functions.

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The Assembly of Porphyrin Systems in Well-Defined Nanostructures: An Update

Molecules ◽

10.3390/molecules24234307 ◽

2019 ◽

Vol 24 (23) ◽

pp. 4307 ◽

Cited By ~ 12

Author(s):

Gabriele Magna ◽

Donato Monti ◽

Corrado Di Natale ◽

Roberto Paolesse ◽

Manuela Stefanelli

Keyword(s):

Self Assembly ◽

Energy Transport ◽

Functional Materials ◽

Building Blocks ◽

Spatial Arrangement ◽

Transport Processes ◽

Internal Electric Field ◽

Porphyrin Derivatives ◽

Molecular Building Blocks ◽

The Individual

The interest in assembling porphyrin derivatives is widespread and is accounted by the impressive impact of these suprastructures of controlled size and shapes in many applications from nanomedicine and sensors to photocatalysis and optoelectronics. The massive use of porphyrin dyes as molecular building blocks of functional materials at different length scales relies on the interdependent pair properties, consisting of their chemical stability/synthetic versatility and their quite unique physicochemical properties. Remarkably, the driven spatial arrangement of these platforms in well-defined suprastructures can synergically amplify the already excellent properties of the individual monomers, improving conjugation and enlarging the intensity of the absorption range of visible light, or forming an internal electric field exploitable in light-harvesting and charge-and energy-transport processes. The countless potentialities offered by these systems means that self-assembly concepts and tools are constantly explored, as confirmed by the significant number of published articles related to porphyrin assemblies in the 2015–2019 period, which is the focus of this review.

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Research progresses on the functional polypeptides in the detection and imaging of breast cancer

Journal of Materials Chemistry B ◽

10.1039/c7tb02541f ◽

2018 ◽

Vol 6 (17) ◽

pp. 2510-2523 ◽

Cited By ~ 8

Author(s):

Jing Zhao ◽

Huinan Chen ◽

Yingying Tang ◽

Hong Chen ◽

Guifang Chen ◽

...

Keyword(s):

Breast Cancer ◽

Functional Groups ◽

Building Blocks ◽

Significant Interest ◽

Recognition Elements ◽

Signal Sources

Polypeptides as functional groups continue to garner significant interest in the detection and imaging of breast cancer, working as recognition elements, signal sources, building blocks and therapeutic reagents, etc.

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Hierarchical assembly of micro-/nano-building blocks: bio-inspired rigid structural functional materials

Chemical Society Reviews ◽

10.1039/c0cs00121j ◽

2011 ◽

Vol 40 (7) ◽

pp. 3764 ◽

Cited By ~ 271

Author(s):

Hong-Bin Yao ◽

Hai-Yu Fang ◽

Xiao-Han Wang ◽

Shu-Hong Yu

Keyword(s):

Functional Materials ◽

Building Blocks ◽

Hierarchical Assembly

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Spectroscopic Characterization of Flame-Generated 2-D Carbon Nano-Disks

MRS Proceedings ◽

10.1557/opl.2015.726 ◽

2015 ◽

Vol 1726 ◽

Author(s):

Patrizia Minutolo ◽

Mario Commodo ◽

Gianluigi De Falco ◽

Rosanna Larciprete ◽

Andrea D'Anna

Keyword(s):

Carbon Nanostructures ◽

Functional Materials ◽

Building Blocks ◽

Spectroscopic Characterization ◽

Molecular Compound ◽

Force Microscopy ◽

Atomic Force ◽

Thin Carbon ◽

On Line ◽

20 Nm

ABSTRACTIn this work we produce atomically thin carbon nanostructures which have a disk-like shape when deposited on a substrate. These nanostructures have intermediate characteristics between a graphene island and a molecular compound and have the potentiality to be used either as they are, or to become building blocks for functional materials or to be manipulated and engineered into composite layered structures.The carbon nanostructures are produced in a premixed ethylene/air flame with a slight excess of fuel with respect to the stoichiometric value. The size distribution of the produced compounds in aerosol phase has been measured on line by means of a differential mobility analyzer (DMA) and topographic images of the structures deposited on mica disks were obtained by Atomic Force Microscopy. Raman spectroscopy and XPS have been used to characterize their structure and the electronic and optical properties were obtained combining on-line photoionization measurements with Cyclic Voltammetry, light absorption and photoluminescence.When deposited on the mica substrate the carbon compounds assume the shape of an atomically thin disk with in plane diameter of about 20 nm. Carbon nano-disks consist of a network of small aromatic island with in plane length, La, of about 1 nm. Raman spectra evidence a significant amount of disorder which is in a large part due to the quantum confinement in the aromatic islands. Nano-disks contain small percentage of sp3 and the O/C ratio is lower than 6%. They furthermore present interesting UV and visible photoluminescence properties.

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