scholarly journals Self-assembly of a strapped linear porphyrin oligomer on HOPG

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Abigail Bellamy-Carter ◽  
Cécile Roche ◽  
Harry L. Anderson ◽  
Alex Saywell
Keyword(s):  
Self Assembly ◽  
Quantum Interference ◽  
Pyrolytic Graphite ◽  
Polymer System ◽  
Emergent Properties ◽  
Tunnelling Microscopy ◽  
Self Assembled ◽  
Molecule Interactions ◽  
Unit Cell Dimensions ◽  
High Degree

AbstractPolymeric structures based on porphyrin units exhibit a range of complex properties, such as nanoscale charge transport and quantum interference effects, and have the potential to act as biomimetic materials for light-harvesting and catalysis. These functionalities are based upon the characteristics of the porphyrin monomers, but are also emergent properties of the extended polymer system. Incorporation of these properties within solid-state devices requires transfer of the polymers to a supporting substrate, and may require a high-degree of lateral order. Here we show that highly ordered self-assembled structures can be formed via a simple solution deposition protocol; for a strapped linear porphyrin oligomer adsorbed on a highly oriented pyrolytic graphite (HOPG) substrate. Two distinct molecule–molecule interactions are observed to drive the formation of two molecular phases (‘Interdigitated’ and ‘Bridge-stabilised’) characterised by scanning tunnelling microscopy, providing information on the unit cell dimensions and self-assembled structure. The concentration dependence of these phases is investigated, and we conclude that the bridge-stabilised phase is a thermodynamically stable structure at room temperature.

scholarly journals STM visualisation of counterions and the effect of charges on self-assembled monolayers of macrocycles

2011 ◽  
Vol 2 ◽  
pp. 674-680 ◽  
Author(s):  
Tibor Kudernac ◽  
Natalia Shabelina ◽  
Wael Mamdouh ◽  
Sigurd Höger ◽  
Steven De Feyter
Keyword(s):  
Self Assembly ◽  
The Self ◽  
Self Assembled Monolayers ◽  
Assembly Process ◽  
Organic Monolayers ◽  
Preferential Adsorption ◽  
Scanning Tunnelling ◽  
Assembled Monolayers ◽  
Tunnelling Microscopy ◽  
Self Assembled

Despite their importance in self-assembly processes, the influence of charged counterions on the geometry of self-assembled organic monolayers and their direct localisation within the monolayers has been given little attention. Recently, various examples of self-assembled monolayers composed of charged molecules on surfaces have been reported, but no effort has been made to prove the presence of counterions within the monolayer. Here we show that visualisation and exact localisation of counterions within self-assembled monolayers can be achieved with scanning tunnelling microscopy (STM). The presence of charges on the studied shape-persistent macrocycles is shown to have a profound effect on the self-assembly process at the liquid–solid interface. Furthermore, preferential adsorption was observed for the uncharged analogue of the macrocycle on a surface.

scholarly journals Self-assembly and wetting properties of gold nanorod–CTAB molecules on HOPG

2019 ◽  
Vol 10 ◽  
pp. 696-705 ◽  
Author(s):  
Imtiaz Ahmad ◽  
Floor Derkink ◽  
Tim Boulogne ◽  
Pantelis Bampoulis ◽  
Harold J W Zandvliet ◽  
...  
Keyword(s):  
Self Assembly ◽  
Cetyltrimethylammonium Bromide ◽  
Pyrolytic Graphite ◽  
The Self ◽  
Gold Nanorod ◽  
Force Microscopy ◽  
Wetting Properties ◽  
Atomic Force ◽  
Highly Ordered Pyrolytic Graphite ◽  
Self Assembled

The formation of self-assembled superstructures of cetyltrimethylammonium bromide (CTAB) after drying on a nonwetting highly ordered pyrolytic graphite (HOPG) surface have been investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Although SEM did not reveal coverage of CTAB layers, AFM showed not only CTAB assembly, but also the dynamics of the process on the surface. The self-assembled layers of CTAB molecules on the HOPG terraces prior to nanorod deposition were shown to change the wettability of the surface, and as a result, gold nanorod deposition takes place on nonwetting HOPG terraces.

Strategies to create hierarchical self-assembled structures via cooperative non-covalent interactions

2015 ◽  
Vol 44 (8) ◽  
pp. 2543-2572 ◽  
Author(s):  
Christina Rest ◽  
Ramesh Kandanelli ◽  
Gustavo Fernández
Keyword(s):  
Self Assembly ◽  
Supramolecular Polymers ◽  
Supramolecular Systems ◽  
Multiple Systems ◽  
Cooperative Phenomena ◽  
Non Covalent Interactions ◽  
Self Assembled ◽  
High Degree ◽  
Covalent Interactions ◽  
Degree Of Order

Cooperative phenomena exhibit the basis for the hierarchical self-assembly of multiple systems in nature. Motivated by the high degree of order in these structures, a large number of supramolecular polymers have been designed whose aggregation follows a cooperative pathway. Herein, we have classified the supramolecular systems depending on the cooperative non-covalent forces driving their formation.

Comparison of TEM and STM observations of small silver clusters on different carbon supports

1990 ◽  
Vol 48 (4) ◽  
pp. 264-265
Author(s):  
Bernd Tesche ◽  
Tobias Schilling
Keyword(s):  
Vibration Isolation ◽  
Pyrolytic Graphite ◽  
Carbon Film ◽  
Silver Clusters ◽  
Carbon Supports ◽  
Stacking Order ◽  
System P ◽  
High Resolution Tem ◽  
High Degree ◽  
Degree Of Order

The objective of our work is to determine:a) whether both of the imaging methods (TEM, STM) yield comparable data andb) which method is better suited for a reliable structure analysis of microclusters smaller than 1.5 nm, where a deviation of the bulk structure is expected.The silver was evaporated in a bell-jar system (p 10−5 pa) and deposited onto a 6 nm thick amorphous carbon film and a freshly cleaved highly oriented pyrolytic graphite (HOPG).The average deposited Ag thickness is 0.1 nm, controlled by a quartz crystal microbalance at a deposition rate of 0.02 nm/sec. The high resolution TEM investigations (100 kV) were executed by a hollow-cone illumination (HCI). For the STM investigations a commercial STM was used. With special vibration isolation we achieved a resolution of 0.06 nm (inserted diffraction image in Fig. 1c). The carbon film shows the remarkable reduction in noise by using HCI (Fig. 1a). The HOPG substrate (Fig. 1b), cleaved in sheets thinner than 30 nm for the TEM investigations, shows the typical arrangement of a nearly perfect stacking order and varying degrees of rotational disorder (i.e. artificial single crystals). The STM image (Fig. 1c) demonstrates the high degree of order in HOPG with atomic resolution.

Nanoscale Self-Assembly Using Ion and Electron Beam Techniques: A Rapid Review

MRS Advances ◽  
2020 ◽  
Vol 5 (64) ◽  
pp. 3507-3520
Author(s):  
Chunhui Dai ◽  
Kriti Agarwal ◽  
Jeong-Hyun Cho
Keyword(s):  
Electron Beam ◽  
Self Assembly ◽  
Ion Beam ◽  
Three Dimensional ◽  
The Self ◽  
Stress Generation ◽  
Rapid Review ◽  
High Yield ◽  
3D Nanostructures ◽  
Self Assembled

AbstractNanoscale self-assembly, as a technique to transform two-dimensional (2D) planar patterns into three-dimensional (3D) nanoscale architectures, has achieved tremendous success in the past decade. However, an assembly process at nanoscale is easily affected by small unavoidable variations in sample conditions and reaction environment, resulting in a low yield. Recently, in-situ monitored self-assembly based on ion and electron irradiation has stood out as a promising candidate to overcome this limitation. The usage of ion and electron beam allows stress generation and real-time observation simultaneously, which significantly enhances the controllability of self-assembly. This enables the realization of various complex 3D nanostructures with a high yield. The additional dimension of the self-assembled 3D nanostructures opens the possibility to explore novel properties that cannot be demonstrated in 2D planar patterns. Here, we present a rapid review on the recent achievements and challenges in nanoscale self-assembly using electron and ion beam techniques, followed by a discussion of the novel optical properties achieved in the self-assembled 3D nanostructures.

Investigation of Au SAMs Photoclick Derivatization by PM-IRRAS

2019 ◽  
Author(s):  
Mark Workentin ◽  
François Lagugné-Labarthet ◽  
Sidney Legge
Keyword(s):  
Cell Adhesion ◽  
Self Assembly ◽  
Materials Science ◽  
Fibroblast Cell ◽  
Fine Tuning ◽  
Chemical System ◽  
Infrared Reflection ◽  
Assembled Monolayers ◽  
One Step ◽  
High Degree

In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>

Self-Assembly of a Chiral Cubic Three-Connected Net from the High Symmetry Molecules C60 and SnI4

2020 ◽  
Author(s):  
Daniel B. Straus ◽  
Robert J. Cava
Keyword(s):  
Organic Synthesis ◽  
Self Assembly ◽  
Van Der Waals ◽  
Van Der Waals Forces ◽  
High Symmetry ◽  
Molecular Chirality ◽  
Chiral Materials ◽  
Self Assembled ◽  
Chiral Centers

The design of new chiral materials usually requires stereoselective organic synthesis to create molecules with chiral centers. Less commonly, achiral molecules can self-assemble into chiral materials, despite the absence of intrinsic molecular chirality. Here, we demonstrate the assembly of high-symmetry molecules into a chiral van der Waals structure by synthesizing crystals of C<sub>60</sub>(SnI<sub>4</sub>)<sub>2</sub> from icosahedral buckminsterfullerene (C<sub>60</sub>) and tetrahedral SnI4 molecules through spontaneous self-assembly. The SnI<sub>4</sub> tetrahedra template the Sn atoms into a chiral cubic three-connected net of the SrSi<sub>2</sub> type that is held together by van der Waals forces. Our results represent the remarkable emergence of a self-assembled chiral material from two of the most highly symmetric molecules, demonstrating that almost any molecular, nanocrystalline, or engineered precursor can be considered when designing chiral assemblies.

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 Nano- and Micropatterning on Optical Fibers by Bottom-Up Approach: The Importance of Being Ordered

2021 ◽  
Vol 11 (7) ◽  
pp. 3254
Author(s):  
Marco Pisco ◽  
Francesco Galeotti
Keyword(s):  
Optical Fiber ◽  
Optical Fibers ◽  
Self Assembly ◽  
Ordered Structures ◽  
Bottom Up ◽  
Photonic Structures ◽  
Fiber Technology ◽  
Optical Fiber Probes ◽  
Fiber Probes ◽  
Self Assembled

The realization of advanced optical fiber probes demands the integration of materials and structures on optical fibers with micro- and nanoscale definition. Although researchers often choose complex nanofabrication tools to implement their designs, the migration from proof-of-principle devices to mass production lab-on-fiber devices requires the development of sustainable and reliable technology for cost-effective production. To make it possible, continuous efforts are devoted to applying bottom-up nanofabrication based on self-assembly to decorate the optical fiber with highly ordered photonic structures. The main challenges still pertain to “order” attainment and the limited number of implementable geometries. In this review, we try to shed light on the importance of self-assembled ordered patterns for lab-on-fiber technology. After a brief presentation of the light manipulation possibilities concerned with ordered structures, and of the new prospects offered by aperiodically ordered structures, we briefly recall how the bottom-up approach can be applied to create ordered patterns on the optical fiber. Then, we present un-attempted methodologies, which can enlarge the set of achievable structures, and can potentially improve the yielding rate in finely ordered self-assembled optical fiber probes by eliminating undesired defects and increasing the order by post-processing treatments. Finally, we discuss the available tools to quantify the degree of order in the obtained photonic structures, by suggesting the use of key performance figures of merit in order to systematically evaluate to what extent the pattern is really “ordered”. We hope such a collection of articles and discussion herein could inspire new directions and hint at best practices to fully exploit the benefits inherent to self-organization phenomena leading to ordered systems.

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