Emergence of complexity in hierarchically organized chiral particles

Science ◽  
2020 ◽  
Vol 368 (6491) ◽  
pp. 642-648 ◽  
Author(s):  
Wenfeng Jiang ◽  
Zhi-bei Qu ◽  
Prashant Kumar ◽  
Drew Vecchio ◽  
Yuefei Wang ◽  
...  
Keyword(s):  
Self Assembly ◽  
Multiple Scales ◽  
Chemical Properties ◽  
Structural Complexity ◽  
Large Family ◽  
Building Blocks ◽  
Geometrical Complexity ◽  
Complex Architectures ◽  
Gold Thiolate ◽  
Emergence Of Complexity

The structural complexity of composite biomaterials and biomineralized particles arises from the hierarchical ordering of inorganic building blocks over multiple scales. Although empirical observations of complex nanoassemblies are abundant, the physicochemical mechanisms leading to their geometrical complexity are still puzzling, especially for nonuniformly sized components. We report the self-assembly of hierarchically organized particles (HOPs) from polydisperse gold thiolate nanoplatelets with cysteine surface ligands. Graph theory methods indicate that these HOPs, which feature twisted spikes and other morphologies, display higher complexity than their biological counterparts. Their intricate organization emerges from competing chirality-dependent assembly restrictions that render assembly pathways primarily dependent on nanoparticle symmetry rather than size. These findings and HOP phase diagrams open a pathway to a large family of colloids with complex architectures and unusual chiroptical and chemical properties.

scholarly journals Expanding the molecular-ruler process through vapor deposition of hexadecanethiol

2017 ◽  
Vol 8 ◽  
pp. 2339-2344 ◽  
Author(s):  
Alexandra M Patron ◽  
Timothy S Hooker ◽  
Daniel F Santavicca ◽  
Corey P Causey ◽  
Thomas J Mullen
Keyword(s):  
Vapor Phase ◽  
Self Assembly ◽  
Chemical Properties ◽  
Solution Deposition ◽  
Precise Control ◽  
Vapor Phase Deposition ◽  
Great Utility ◽  
Complex Architectures ◽  
Molecular Ruler ◽  
Physical And Chemical

The development of methods to produce nanoscale features with tailored chemical functionalities is fundamental for applications such as nanoelectronics and sensor fabrication. The molecular-ruler process shows great utility for this purpose as it combines top-down lithography for the creation of complex architectures over large areas in conjunction with molecular self-assembly, which enables precise control over the physical and chemical properties of small local features. The molecular-ruler process, which most commonly uses mercaptoalkanoic acids and metal ions to generate metal-ligated multilayers, can be employed to produce registered nanogaps between metal features. Expansion of this methodology to include molecules with other chemical functionalities could greatly expand the overall versatility, and thus the utility, of this process. Herein, we explore the use of alkanethiol molecules as the terminating layer of metal-ligated multilayers. During this study, it was discovered that the solution deposition of alkanethiol molecules resulted in low overall surface coverage with features that varied in height. Because features with varied heights are not conducive to the production of uniform nanogaps via the molecular-ruler process, the vapor-phase deposition of alkanethiol molecules was explored. Unlike the solution-phase deposition, alkanethiol islands produced by vapor-phase deposition exhibited markedly higher surface coverages of uniform heights. To illustrate the applicability of this method, metal-ligated multilayers, both with and without an alkanethiol capping layer, were utilized to create nanogaps between Au features using the molecular-ruler process.

scholarly journals Beyond icosahedral symmetry in packings of proteins in spherical shells

2017 ◽  
Vol 114 (34) ◽  
pp. 9014-9019 ◽  
Author(s):  
Majid Mosayebi ◽  
Deborah K. Shoemark ◽  
Jordan M. Fletcher ◽  
Richard B. Sessions ◽  
Noah Linden ◽  
...  
Keyword(s):  
Self Assembly ◽  
De Novo ◽  
Multiple Scales ◽  
Building Blocks ◽  
Icosahedral Symmetry ◽  
Protein Cages ◽  
Natural Systems ◽  
Wide Range ◽  
Stable Arrangement ◽  
Symmetric Structures

The formation of quasi-spherical cages from protein building blocks is a remarkable self-assembly process in many natural systems, where a small number of elementary building blocks are assembled to build a highly symmetric icosahedral cage. In turn, this has inspired synthetic biologists to design de novo protein cages. We use simple models, on multiple scales, to investigate the self-assembly of a spherical cage, focusing on the regularity of the packing of protein-like objects on the surface. Using building blocks, which are able to pack with icosahedral symmetry, we examine how stable these highly symmetric structures are to perturbations that may arise from the interplay between flexibility of the interacting blocks and entropic effects. We find that, in the presence of those perturbations, icosahedral packing is not the most stable arrangement for a wide range of parameters; rather disordered structures are found to be the most stable. Our results suggest that (i) many designed, or even natural, protein cages may not be regular in the presence of those perturbations and (ii) optimizing those flexibilities can be a possible design strategy to obtain regular synthetic cages with full control over their surface properties.

scholarly journals Supramolecular Structures and Self-Association Processes in Polymer Systems

2016 ◽  
pp. S165-S178 ◽  
Author(s):  
M. HRUBÝ ◽  
S. K. FILIPPOV ◽  
P. ŠTĚPÁNEK
Keyword(s):  
Self Assembly ◽  
Targeted Delivery ◽  
Aqueous Media ◽  
Polymer System ◽  
Chemical Properties ◽  
Building Blocks ◽  
Self Organization ◽  
Triggered Release ◽  
Polymer Systems ◽  
Self Association

Self-organization in a polymer system appears when a balance is achieved between long-range repulsive and short-range attractive forces between the chemically different building blocks. Block copolymers forming supramolecular assemblies in aqueous media represent materials which are extremely useful for the construction of drug delivery systems especially for cancer applications. Such formulations suppress unwanted physico-chemical properties of the encapsulated drugs, modify biodistribution of the drugs towards targeted delivery into tissue of interest and allow triggered release of the active cargo. In this review, we focus on general principles of polymer self-organization in solution, phase separation in polymer systems (driven by external stimuli, especially by changes in temperature, pH, solvent change and light) and on effects of copolymer architecture on the self-assembly process.

Functional self-assembling polypeptide bionanomaterials

2012 ◽  
Vol 40 (4) ◽  
pp. 629-634 ◽  
Author(s):  
Tibor Doles ◽  
Sabina Božič ◽  
Helena Gradišar ◽  
Roman Jerala
Keyword(s):  
Self Assembly ◽  
Biological Systems ◽  
Three Dimensional ◽  
Coiled Coil ◽  
Chemical Properties ◽  
Building Blocks ◽  
External Signal ◽  
Form Complex ◽  
Cell Factories ◽  
Self Assembling

Bionanotechnology seeks to modify and design new biopolymers and their applications and uses biological systems as cell factories for the production of nanomaterials. Molecular self-assembly as the main organizing principle of biological systems is also the driving force for the assembly of artificial bionanomaterials. Protein domains and peptides are particularly attractive as building blocks because of their ability to form complex three-dimensional assemblies from a combination of at least two oligomerization domains that have the oligomerization state of at least two and three respectively. In the present paper, we review the application of polypeptide-based material for the formation of material with nanometre-scale pores that can be used for the separation. Use of antiparallel coiled-coil dimerization domains introduces the possibility of modulation of pore size and chemical properties. Assembly or disassembly of bionanomaterials can be regulated by an external signal as demonstrated by the coumermycin-induced dimerization of the gyrase B domain which triggers the formation of polypeptide assembly.

scholarly journals A Novel 3d-4f CoII-GdIII system with 4,5-imidazoledicarboxylate and oxalate

2014 ◽  
Vol 70 (a1) ◽  
pp. C1721-C1721
Author(s):  
Andrés Vega ◽  
Carlos Cruz ◽  
Verónica Paredes-García ◽  
Evgenia Spodine ◽  
Diego Venegas-Yazigi
Keyword(s):  
Phase 1 ◽  
Chemical Properties ◽  
Structural Complexity ◽  
Building Blocks ◽  
Point Of View ◽  
Advanced Materials ◽  
Water Molecules ◽  
New Materials ◽  
Metal Centers ◽  
Physical And Chemical

The challenges of designing and synthesizing new materials, the complexity of their structures, and their potential physical properties have continued to attract a great deal of interest. The combination of organic and inorganic components into the same molecular backbone has captivated many researchers, and as a consequence of the multiple choices of the components and also of the used synthetic strategies, a wide variety of advanced materials has been obtained. In many cases, an increase in structural complexity gives rise to new properties, which cannot be foreseen on the basis of the single constituting moieties. Therefore, the assembly of different components, or molecular fragments, may give rise to new materials that exhibit interesting and useful physical and chemical properties in the condensed phase.1 From a structural and synthetic point of view, the literature shows that a wide variety of polymetallic systems ranging from 0D to 3D structures have been rationally designed and synthesized by the appropriate selection of the metal centers and organic building blocks, as well as of the reaction pathways.2 In this work, we will inform the synthesis and structural characterization of a novel 3d-4f bimetallic system: {[Co(H2O)2(ImDC)Gd(ox)2(H2O)]·2H2O}n. (ImDC: 4,5-imidazoledicarboxylate; ox: oxalate). The structure displays CoII cations having an approximately octahedral environment completed by two N,O-ImDC ligands and two water molecules, while the GdIII cations displays nine coordination completed exclusively by oxygen atoms coming from a water molecule and oxalate and ImDC anions (Figure1, left). The structure defines a covalent tridimensional lattice where two water molecules by formula are trapped inside the cavities left by this arrangement (Figure1, right). Figure 1: Structural diagram for the basic bimetallic unit Co(H2O)2(ImDC)Gd(ox)2(H2O) (left) and the packing showing trapped water molecules {[Co(H2O)2(ImDC)Gd(ox)2(H2O)]·2H2O}n (right). Acknowledgements: The authors acknowledge financial support from FONDECYT 1130643, Financiamiento Basal, FB0807. C.C. thanks CONICYT Fellowship.

Factors Affecting Molecular Self-Assembly and Its Mechanism

2012 ◽  
Vol 9 (1) ◽  
pp. 43 ◽  
Author(s):  
Hueyling Tan
Keyword(s):  
Self Assembly ◽  
Building Blocks ◽  
Molecular Engineering ◽  
Molecular Structures ◽  
Polymer Science ◽  
New Approach ◽  
Factors Affecting ◽  
Dna Structures ◽  
Self Assembling ◽  
Wide Range

Molecular self-assembly is ubiquitous in nature and has emerged as a new approach to produce new materials in chemistry, engineering, nanotechnology, polymer science and materials. Molecular self-assembly has been attracting increasing interest from the scientific community in recent years due to its importance in understanding biology and a variety of diseases at the molecular level. In the last few years, considerable advances have been made in the use ofpeptides as building blocks to produce biological materials for wide range of applications, including fabricating novel supra-molecular structures and scaffolding for tissue repair. The study ofbiological self-assembly systems represents a significant advancement in molecular engineering and is a rapidly growing scientific and engineering field that crosses the boundaries ofexisting disciplines. Many self-assembling systems are rangefrom bi- andtri-block copolymers to DNA structures as well as simple and complex proteins andpeptides. The ultimate goal is to harness molecular self-assembly such that design andcontrol ofbottom-up processes is achieved thereby enabling exploitation of structures developed at the meso- and macro-scopic scale for the purposes oflife and non-life science applications. Such aspirations can be achievedthrough understanding thefundamental principles behind the selforganisation and self-synthesis processes exhibited by biological systems.

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.

Reversible microscale assembly of nanoparticles driven by the phase transition of a thermotropic liquid crystal

2017 ◽  
Author(s):  
Niamh Mac Fhionnlaoich ◽  
Stephen Schrettl ◽  
Nicholas B. Tito ◽  
Ye Yang ◽  
Malavika Nair ◽  
...  
Keyword(s):  
Phase Transition ◽  
Liquid Crystal ◽  
Self Assembly ◽  
Nematic Phase ◽  
Hierarchical Control ◽  
Building Blocks ◽  
Model System ◽  
Microscopic Level ◽  
Reversible Process ◽  
Thermotropic Liquid Crystal

The arrangement of nanoscale building blocks into patterns with microscale periodicity is challenging to achieve via self-assembly processes. Here, we report on the phase transition-driven collective assembly of gold nanoparticles in a thermotropic liquid crystal. A temperature-induced transition from the isotropic to the nematic phase leads to the assembly of individual nanometre-sized particles into arrays of micrometre-sized aggregates, whose size and characteristic spacing can be tuned by varying the cooling rate. This fully reversible process offers hierarchical control over structural order on the molecular, nanoscopic, and microscopic level and is an interesting model system for the programmable patterning of nanocomposites with access to micrometre-sized periodicities.

Dibenzochrysene Enables Tightly Controlled Docking and Stabilizes Photoexcited States in Dual-Pore Covalent Organic Frameworks

2019 ◽  
Author(s):  
Torben Sick ◽  
Niklas Keller ◽  
Nicolai Bach ◽  
Andreas Koszalkowski ◽  
Julian Rotter ◽  
...  
Keyword(s):  
Molecular Docking ◽  
Photophysical Properties ◽  
Visible Spectrum ◽  
Large Family ◽  
Building Blocks ◽  
Band Gaps ◽  
Docking Site ◽  
Covalent Organic Frameworks ◽  
Connected Node ◽  
Optoelectronic Applications

Covalent organic frameworks (COFs), consisting of covalently connected organic building units, combine attractive features such as crystallinity, open porosity and widely tunable physical properties. For optoelectronic applications, the incorporation of heteroatoms into a 2D COF has the potential to yield desired photophysical properties such as lower band gaps, but can also cause lateral offsets of adjacent layers. Here, we introduce dibenzo[g,p]chrysene (DBC) as a novel building block for the synthesis of highly crystalline and porous 2D dual-pore COFs showing interesting properties for optoelectronic applications. The newly synthesized terephthalaldehyde (TA), biphenyl (Biph), and thienothiophene (TT) DBC-COFs combine conjugation in the a,b-plane with a tight packing of adjacent layers guided through the molecular DBC node serving a specific docking site for successive layers. The resulting DBC-COFs exhibit a hexagonal dual-pore kagome geometry, which is comparable to COFs containing another molecular docking site, namely 4,4′,4″,4‴-(ethylene-1,1,2,2-tetrayl)-tetraaniline (ETTA). In this context, the respective interlayer distances decrease from about 4.60 Å in ETTA-COFs to about 3.6 Å in DBC-COFs, leading to well-defined hexagonally faceted single crystals sized about 50-100 nm. The TT DBC-COFs feature broad light absorption covering large parts of the visible spectrum, while Biph DBC-COF shows extraordinary excited state lifetimes exceeding 10 ns. In combination with the large number of recently developed linear conjugated building blocks, the new DBC tetra-connected node is expected to enable the synthesis of a large family of strongly p-stacked, highly ordered 2D COFs with promising optoelectronic properties.

scholarly journals Synthesis and Self-assembly of Amphiphilic Precision Glycomacromolecules

2021 ◽  
Author(s):  
Alexander Banger ◽  
Julian Sindram ◽  
Marius Otten ◽  
Jessica Kania ◽  
Alexander Strzelczyk ◽  
...  
Keyword(s):  
Self Assembly ◽  
Solid Phase ◽  
Building Blocks ◽  
Polymer Synthesis

We present the synthesis of so called amphiphilic glycomacromolecules (APGs) by using solid-phase polymer synthesis. Based on tailor made building blocks, monosdisperse APGs with varying compositions are synthesized, introducing carbohydrate...

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