A Bottom-Up Approach to Solution-Processed, Atomically Precise Graphitic Cylinders on Surfaces

2018 ◽  
Author(s):  
Erik Leonhardt ◽  
Jeff M. Van Raden ◽  
David Miller ◽  
Lev N. Zakharov ◽  
Benjamin Aleman ◽  
...  
Keyword(s):  
Self Assembly ◽  
Carbon Nanostructures ◽  
Carbon Nanomaterials ◽  
Circle Packing ◽  
Pyrolytic Graphite ◽  
Building Blocks ◽  
Bottom Up ◽  
Casting Technique ◽  
New Class ◽  
Solution Casting Technique

Extended carbon nanostructures, such as carbon nanotubes (CNTs), exhibit remarkable properties but are difficult to synthesize uniformly. Herein, we present a new class of carbon nanomaterials constructed via the bottom-up self-assembly of cylindrical, atomically-precise small molecules. Guided by supramolecular design principles and circle packing theory, we have designed and synthesized a fluorinated nanohoop that, in the solid-state, self-assembles into nanotube-like arrays with channel diameters of precisely 1.63 nm. A mild solution-casting technique is then used to construct vertical “forests” of these arrays on a highly-ordered pyrolytic graphite (HOPG) surface through epitaxial growth. Furthermore, we show that a basic property of nanohoops, fluorescence, is readily transferred to the bulk phase, implying that the properties of these materials can be directly altered via precise functionalization of their nanohoop building blocks. The strategy presented is expected to have broader applications in the development of new graphitic nanomaterials with π-rich cavities reminiscent of CNTs.

A Bottom-Up Approach to Solution-Processed, Atomically Precise Graphitic Cylinders on Surfaces

2018 ◽  
Author(s):  
Erik Leonhardt ◽  
Jeff M. Van Raden ◽  
David Miller ◽  
Lev N. Zakharov ◽  
Benjamin Aleman ◽  
...  
Keyword(s):  
Self Assembly ◽  
Carbon Nanostructures ◽  
Carbon Nanomaterials ◽  
Circle Packing ◽  
Pyrolytic Graphite ◽  
Building Blocks ◽  
Bottom Up ◽  
Casting Technique ◽  
New Class ◽  
Solution Casting Technique

Extended carbon nanostructures, such as carbon nanotubes (CNTs), exhibit remarkable properties but are difficult to synthesize uniformly. Herein, we present a new class of carbon nanomaterials constructed via the bottom-up self-assembly of cylindrical, atomically-precise small molecules. Guided by supramolecular design principles and circle packing theory, we have designed and synthesized a fluorinated nanohoop that, in the solid-state, self-assembles into nanotube-like arrays with channel diameters of precisely 1.63 nm. A mild solution-casting technique is then used to construct vertical “forests” of these arrays on a highly-ordered pyrolytic graphite (HOPG) surface through epitaxial growth. Furthermore, we show that a basic property of nanohoops, fluorescence, is readily transferred to the bulk phase, implying that the properties of these materials can be directly altered via precise functionalization of their nanohoop building blocks. The strategy presented is expected to have broader applications in the development of new graphitic nanomaterials with π-rich cavities reminiscent of CNTs.

scholarly journals Nanoscale Crystalline Sheets and Vesicles Assembled from Nonplanar Cyclic π-Conjugated Molecules

Research ◽  
2019 ◽  
Vol 2019 ◽  
pp. 1-11 ◽  
Author(s):  
Huang Tang ◽  
Zhewei Gu ◽  
Haifeng Ding ◽  
Zhibo Li ◽  
Shiyan Xiao ◽  
...  
Keyword(s):  
Self Assembly ◽  
Carbon Nanomaterials ◽  
Materials Science ◽  
Functional Materials ◽  
Building Blocks ◽  
Molecular Scaffolds ◽  
Conjugated Molecules ◽  
New Class ◽  
Supramolecular Architectures ◽  
Cyclic Molecules

A fundamental challenge in chemistry and materials science is to create new carbon nanomaterials by assembling structurally unique carbon building blocks, such as nonplanar π-conjugated cyclic molecules. However, self-assembly of such cyclic π-molecules to form organized nanostructures has been rarely explored despite intensive studies on their chemical synthesis. Here we synthesized a family of new cycloparaphenylenes and found that these fully hydrophobic and nonplanar cyclic π-molecules could self-assemble into structurally distinct two-dimensional crystalline multilayer nanosheets. Moreover, these crystalline multilayer nanosheets could overcome inherent rigidity to curve into closed crystalline vesicles in solution. These supramolecular assemblies show that the cyclic molecular scaffolds are homogeneously arranged on the surface of nanosheets and vesicles with their molecular isotropic x-y plane standing obliquely on the surface. These supramolecular architectures that combined exact crystalline order, orientation-specific arrangement of π-conjugated cycles, controllable morphology, uniform molecular pore, superior florescence quench ability, and photoluminescence are expected to give rise to a new class of functional materials displaying unique photonic, electronic, and biological functions.

scholarly journals Self-Assembling Peptides and Carbon Nanomaterials Join Forces for Innovative Biomedical Applications

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4084
Author(s):  
Petr Rozhin ◽  
Costas Charitidis ◽  
Silvia Marchesan
Keyword(s):  
Carbon Nanostructures ◽  
Biomedical Applications ◽  
Carbon Nanomaterials ◽  
Chemical Properties ◽  
Building Blocks ◽  
Research Areas ◽  
Self Assembling ◽  
Concise Review ◽  
Physico Chemical ◽  
Great Progress

Self-assembling peptides and carbon nanomaterials have attracted great interest for their respective potential to bring innovation in the biomedical field. Combination of these two types of building blocks is not trivial in light of their very different physico-chemical properties, yet great progress has been made over the years at the interface between these two research areas. This concise review will analyze the latest developments at the forefront of research that combines self-assembling peptides with carbon nanostructures for biological use. Applications span from tissue regeneration, to biosensing and imaging, and bioelectronics.

Self-assembled plasmonic metamaterials

Nanophotonics ◽  
2013 ◽  
Vol 2 (3) ◽  
pp. 211-240 ◽  
Author(s):  
Stefan Mühlig ◽  
Alastair Cunningham ◽  
José Dintinger ◽  
Toralf Scharf ◽  
Thomas Bürgi ◽  
...  
Keyword(s):  
Self Assembly ◽  
Degrees Of Freedom ◽  
Building Blocks ◽  
Spatial Arrangement ◽  
Plasmonic Nanostructures ◽  
Bottom Up ◽  
Unit Cells ◽  
Amorphous Structures ◽  
Self Assembled ◽  
Novel Applications

AbstractNowadays for the sake of convenience most plasmonic nanostructures are fabricated by top-down nanofabrication technologies. This offers great degrees of freedom to tailor the geometry with unprecedented precision. However, it often causes disadvantages as well. The structures available are usually planar and periodically arranged. Therefore, bulk plasmonic structures are difficult to fabricate and the periodic arrangement causes undesired effects, e.g., strong spatial dispersion is observed in metamaterials. These limitations can be mitigated by relying on bottom-up nanofabrication technologies. There, self-assembly methods and techniques from the field of colloidal nanochemistry are used to build complex functional unit cells in solution from an ensemble of simple building blocks, i.e., in most cases plasmonic nanoparticles. Achievable structures are characterized by a high degree of nominal order only on a short-range scale. The precise spatial arrangement across larger dimensions is not possible in most cases; leading essentially to amorphous structures. Such self-assembled nanostructures require novel analytical means to describe their properties, innovative designs of functional elements that possess a desired near- and far-field response, and entail genuine nanofabrication and characterization techniques. Eventually, novel applications have to be perceived that are adapted to the specifics of the self-assembled nanostructures. This review shall document recent progress in this field of research. Emphasis is put on bottom-up amorphous metamaterials. We document the state-of-the-art but also critically assess the problems that have to be overcome.

scholarly journals Construction of 2D nanoporous networks by coupling on-surface dynamic imine chemistry and dipole-stabilized self-assembly

2017 ◽  
Vol 53 (2) ◽  
pp. 428-431 ◽  
Author(s):  
Jie-Yu Yue ◽  
Marios Markoulides ◽  
Andrew C. Regan ◽  
Shu-Ying Li ◽  
Nikos Chronakis ◽  
...  
Keyword(s):  
Schiff Base ◽  
Self Assembly ◽  
Pyrolytic Graphite ◽  
Building Blocks ◽  
Highly Oriented Pyrolytic Graphite ◽  
Surface Dynamic

Double-walled nanoporous networks based on the Schiff base reaction of nonplanar tripodic building blocks and subsequent dipole-directed self-assembly were fabricated on highly oriented pyrolytic graphite (HOPG).

scholarly journals Quick self-assembly of bio-inspired multi-dimensional well-ordered structures induced by ultrasonic wave energy

PLoS ONE ◽  
2021 ◽  
Vol 16 (2) ◽  
pp. e0246453
Author(s):  
Connor Murphy ◽  
Yunqi Cao ◽  
Nelson Sepúlveda ◽  
Wei Li
Keyword(s):  
Ultrasonic Wave ◽  
Wave Energy ◽  
Self Assembly ◽  
Mechanical Vibration ◽  
Water Environment ◽  
Three Dimensional ◽  
Building Blocks ◽  
Two Dimensional ◽  
Ordered Structures ◽  
Bottom Up

Bottom-up self-assembly of components, inspired by hierarchically self-regulating aggregation of small subunits observed in nature, provides a strategy for constructing two- or three-dimensional intriguing biomimetic materials via the spontaneous combination of discrete building blocks. Herein, we report the methods of ultrasonic wave energy-assisted, fast, two- and three-dimensional mesoscale well-ordered self-assembly of microfabricated building blocks (100 μm in size). Mechanical vibration energy-driven self-assembly of microplatelets at the water-air interface of inverted water droplets is demonstrated, and the real-time formation process of the patterned structure is dynamically explored. 40 kHz ultrasonic wave is transferred into microplatelets suspended in a water environment to drive the self-assembly of predesigned well-ordered structures. Two-dimensional self-assembly of microplatelets inside the water phase with a large patterned area is achieved. Stable three-dimensional multi-layered self-assembled structures are quickly formed at the air-water interface. These demonstrations aim to open distinctive and effective ways for new two-dimensional surface coating technology with autonomous organization strategy, and three-dimensional complex hierarchical architectures built by the bottom-up method and commonly found in nature (such as nacre, bone or enamel, etc.).

scholarly journals Xanthene[n]arenes: Exceptionally Large, Bowl-shaped Macrocyclic Building Blocks Suitable for Self-Assembly

2021 ◽  
Author(s):  
Jonathan Pfeuffer-Rooschüz ◽  
Alessandro Prescimone ◽  
Konrad Tiefenbacher
Keyword(s):  
Self Assembly ◽  
Building Blocks ◽  
The Novel ◽  
Supramolecular Systems ◽  
Binding Properties ◽  
Molecular Capsules ◽  
New Class ◽  
Guest Binding ◽  
Non Covalent Interactions ◽  
Covalent Interactions

<div>A new class of macrocycles denoted as “xanthene[n]arenes” was synthesized. In contrast to most other macrocycles, they feature a rigid bowl-shape, required for the synthesis of cavitands and for the self-assembly to molecular capsules via non-covalent interactions. The derivatization potential of the novel macrocycles was demonstrated on the xanthene[3]arene scaffold. Beside a deep cavitand, a modified macrocycle was synthesized that self-assembles into a hydrogen-bonded tetrameric capsule. Both supramolecular systems display host-guest binding properties, demonstrating the potential of xanthene[n]arenes as a new set of macrocyclic building blocks.</div>

scholarly journals Bottom-Up Fabrication of Protein Nanowires via Controlled Self-Assembly of Recombinant Geobacter Pilins

mBio ◽  
2019 ◽  
Vol 10 (6) ◽  
Author(s):  
K. M. Cosert ◽  
Angelines Castro-Forero ◽  
Rebecca J. Steidl ◽  
Robert M. Worden ◽  
G. Reguera
Keyword(s):  
Electronic Properties ◽  
Self Assembly ◽  
Building Blocks ◽  
Geobacter Sulfurreducens ◽  
Helical Conformation ◽  
High Yield ◽  
Efficient Production ◽  
Bottom Up ◽  
Content Type

ABSTRACT Metal-reducing bacteria in the genus Geobacter use a complex protein apparatus to guide the self-assembly of a divergent type IVa pilin peptide and synthesize conductive pilus appendages that show promise for the sustainable manufacturing of protein nanowires. The preferential helical conformation of the Geobacter pilin, its high hydrophobicity, and precise distribution of charged and aromatic amino acids are critical for biological self-assembly and conductivity. We applied this knowledge to synthesize via recombinant methods truncated pilin peptides for the bottom-up fabrication of protein nanowires and identified rate-limiting steps of pilin nucleation and fiber elongation that control assembly efficiency and nanowire length, respectively. The synthetic fibers retained the biochemical and electronic properties of the native pili even under chemical fixation, a critical consideration for integration of the nanowires into electronic devices. The implications of these results for the design and mass production of customized protein nanowires for diverse applications are discussed. IMPORTANCE The discovery in 2005 of conductive protein appendages (pili) in the metal-reducing bacterium Geobacter sulfurreducens challenged our understanding of biological electron transfer and pioneered studies in electromicrobiology that revealed the electronic basis of many microbial metabolisms and interactions. The protein nature of the pili afforded opportunities for engineering novel conductive peptides for the synthesis of nanowires via cost-effective and scalable manufacturing approaches. However, methods did not exist for efficient production, purification, and in vitro assembly of pilins into nanowires. Here we describe platforms for high-yield recombinant synthesis of Geobacter pilin derivatives and their assembly as protein nanowires with biochemical and electronic properties rivaling those of the native pili. The bottom-up fabrication of protein nanowires exclusively from pilin building blocks confirms unequivocally the charge transport capacity of the peptide assembly and establishes the intellectual foundation needed to manufacture pilin-based nanowires in bioelectronics and other applications.

scholarly journals Septipyridines as conformationally controlled substitutes for inaccessible bis(terpyridine)-derived oligopyridines in two-dimensional self-assembly

2011 ◽  
Vol 2 ◽  
pp. 405-415 ◽  
Author(s):  
Daniel Caterbow ◽  
Daniela Künzel ◽  
Michael G Mavros ◽  
Axel Groß ◽  
Katharina Landfester ◽  
...  
Keyword(s):  
Self Assembly ◽  
Pyrolytic Graphite ◽  
Scanning Tunneling ◽  
Strong Impact ◽  
Tunneling Microscopy ◽  
New Class ◽  
Self Assembling ◽  
Assembly Behavior ◽  
Structure Calculations ◽  
Transoid Conformation

The position of the peripheral nitrogen atoms in bis(terpyridine)-derived oligopyridines (BTPs) has a strong impact on their self-assembly behavior at the liquid/HOPG (highly oriented pyrolytic graphite) interface. The intermolecular hydrogen bonding interactions in these peripheral pyridine units show specific 2D structures for each BTP isomer. From nine possible constitutional isomers only four have been described in the literature. The synthesis and self-assembling behavior of an additional isomer is presented here, but the remaining four members of the series are synthetically inaccessible. The self-assembling properties of three of the missing four BTP isomers can be mimicked by making use of the energetically preferred N–C–C–N transoid conformation between 2,2'-bipyridine subunits in a new class of so-called septipyridines. The structures are investigated by scanning tunneling microscopy (STM) and a combination of force-field and first-principles electronic structure calculations.

scholarly journals Two-dimensional self-assemblies of telechelic organic compounds: structure and surface host–guest chemistry

2013 ◽  
Vol 371 (2000) ◽  
pp. 20120302 ◽  
Author(s):  
Hui-Juan Yan ◽  
Jia Liu ◽  
Dong Wang ◽  
Li-Jun Wan
Keyword(s):  
Hydrogen Bond ◽  
Self Assembly ◽  
Pyrolytic Graphite ◽  
Building Blocks ◽  
Carboxyl Groups ◽  
Two Dimensional ◽  
Guest Molecules ◽  
Surface And Interface ◽  
Trimesic Acid ◽  
Application Fields

Guiding the self-assembly of different types of functional molecules into well-defined structures on surfaces is beneficial for both fundamental surface and interface study and emerging application fields, especially molecular and organic electronics. This review focuses on understanding the two-dimensional self-assembly process of telechelic organics, which feature alkoxylene chains terminated with carboxyl groups. With the combined flexibility of alkyl chains and directionality of carboxyl groups, telechelic organics show unique assembly behaviour on two-dimensional surfaces. By increasing the length of the alkoxylene chains, the cavities in the nanoporous networks of telechelic trimesic acid (1,3,5-benzene tricarboxylic acid) derivatives change from hexagonal cavities to irregular cavities on a highly oriented pyrolytic graphite surface. The nanoporous networks provide a flexible host template for host–guest supramolecular chemistry because the cavities framed by the flexible alkoxylene chains can be changed in accordance with the sizes/shapes of the guest molecules. Furthermore, the terminal carboxylic group can form a hydrogen bond with another hydrogen bond partner, leading to multi-component structural motifs and hierarchical assemblies. The unique assembly behaviour of telechelic organics makes them promising structures as important building blocks for the design and construction of complex self-assembled nanoarchitectures.

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