Biomimetic Mineralization/Synthesis of Mesoscale Order in Hybrid Inorganic–Organic Materials via Nanoparticle Self-Assembly

MRS Bulletin ◽  
2005 ◽  
Vol 30 (10) ◽  
pp. 727-735 ◽  
Author(s):  
Helmut Cölfen ◽  
Shu-Hong Yu
Keyword(s):  
Self Assembly ◽  
Organic Materials ◽  
Complex Form ◽  
Building Blocks ◽  
Advanced Materials ◽  
Biomimetic Mineralization ◽  
Length Scales ◽  
Natural Systems ◽  
Organic Hybrid ◽  
Complex Forms

AbstractThe organization of nanostructures across several length scales by self-assembly is a key challenge in the design of advanced materials. In meeting this challenge, materials scientists can learn much from biomineralization processes in nature. These processes result in hybrid inorganic–organic materials with exquisite and optimized properties, complex forms, and hierarchical order over extended length scales.Biominerals are usually produced in the presence of an insoluble organic template as well as soluble molecules, which control inorganic crystallization, growth, and selfassembly. These processes can be mimicked successfully, resulting in inorganic–organic hybrid materials with complex form and mesoscale order via a nanoparticle selfassembly process.Various strategies can be applied, including the balancing of aggregation and crystallization, transforming and reorganizing of pre-formed nanoparticle building blocks, and face-selective coding of nanoparticle surfaces by additives for controlled self-assembly. The underlying principles of biomimetic mineralization will be described, along with selected examples showing that while much has already been achieved, the perfection of natural systems is still out of reach.

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 DNA–melamine hybrid molecules: from self-assembly to nanostructures

2015 ◽  
Vol 6 ◽  
pp. 1432-1438 ◽  
Author(s):  
Rina Kumari ◽  
Shib Shankar Banerjee ◽  
Anil K Bhowmick ◽  
Prolay Das
Keyword(s):  
Self Assembly ◽  
Coupling Reaction ◽  
Building Blocks ◽  
The Self ◽  
Organic Hybrid ◽  
Molecular Building Blocks ◽  
Cross Coupling Reaction ◽  
Linear Chains ◽  
Hybrid Molecules ◽  
Dna Strands

Single-stranded DNA–melamine hybrid molecular building blocks were synthesized using a phosphoramidation cross-coupling reaction with a zero linker approach. The self-assembly of the DNA–organic hybrid molecules was achieved by DNA hybridization. Following self-assembly, two distinct types of nanostructures in the form of linear chains and network arrays were observed. The morphology of the self-assembled nanostructures was found to depend on the number of DNA strands that were attached to a single melamine molecule.

scholarly journals Lead Selenide Nanostructures Self-Assembled across Multiple Length Scales and Dimensions

2016 ◽  
Vol 2016 ◽  
pp. 1-6 ◽  
Author(s):  
Evan K. Wujcik ◽  
Stephanie R. Aceto ◽  
Radha Narayanan ◽  
Arijit Bose
Keyword(s):  
Self Assembly ◽  
Solution Process ◽  
Lead Selenide ◽  
Advanced Materials ◽  
Device Performance ◽  
Length Scales ◽  
Multiple Length Scales ◽  
Multiple Dimensions ◽  
Self Assembled ◽  
Electronic Technologies

A self-assembly approach to lead selenide (PbSe) structures that have organized across multiple length scales and multiple dimensions has been achieved. These structures consist of angstrom-scale 0D PbSe crystals, synthesized via a hot solution process, which have stacked into 1D nanorods via aligned dipoles. These 1D nanorods have arranged into nanoscale 2D sheets via directional short-ranged attraction. The nanoscale 2D sheets then further aligned into larger 2D microscale planes. In this study, the authors have characterized the PbSe structures via normal and cryo-TEM and EDX showing that this multiscale multidimensional self-assembled alignment is not due to drying effects. These PbSe structures hold promise for applications in advanced materials—particularly electronic technologies, where alignment can aid in device performance.

FINITE ELEMENT SIMULATIONS ON MECHANICAL SELF-ASSEMBLY OF BIOMIMETIC HELICAL STRUCTURES

2013 ◽  
Vol 13 (06) ◽  
pp. 1340018 ◽  
Author(s):  
QIAOHANG GUO ◽  
HUANG ZHENG ◽  
WENZHE CHEN ◽  
ZI CHEN
Keyword(s):  
Drug Delivery ◽  
Finite Element ◽  
Self Assembly ◽  
Building Blocks ◽  
Finite Element Simulations ◽  
Three Dimensions ◽  
Nanoelectromechanical Systems ◽  
Helical Structures ◽  
Thin Structures ◽  
Natural Systems

Helices are ubiquitous building blocks in natural systems, and have since become major sources of inspiration for engineering design of helical devices with a range of applications in sensors, transducers, transistors and micro-robotics devices. In this work, we illustrate the mechanical self-assembly principle in spontaneous helical structures, and perform finite element simulations to model such large deformation of thin structures in three dimensions. Our work can facilitate designs of tunable helical structures at both macroscopic and microscopic scales with desirable geometric parameters for engineering applications such as in nanoelectromechanical systems (NEMS), drug delivery, sensors, acturators, optoelectronics and microbotics.

Assembling Photo- and Electroresponsive Molecules and Nano-Objects

MRS Bulletin ◽  
2007 ◽  
Vol 32 (7) ◽  
pp. 556-560 ◽  
Author(s):  
Michael Busby ◽  
Luisa De Cola ◽  
Gregg S. Kottas ◽  
Zoran Popović
Keyword(s):  
Self Assembly ◽  
Building Blocks ◽  
Supramolecular Systems ◽  
Natural Systems ◽  
Design And Synthesis ◽  
Zeolite L ◽  
Solid Substrates ◽  
Potential Applications ◽  
Collective Interactions ◽  
Spectroscopic Behavior

The self-assembly of small molecules into large, functional nanostructures has led to the construction of supramolecular systems, both in solution and on solid substrates, with defined dimensions that display unique properties through collective interactions, much like natural systems. In this article, we show how one assembles photo- and electroluminescent molecules through coordination chemistry for the purpose of producing novel materials that can be used for displays and lighting applications. In a stepwise process, we discuss the design and synthesis of the components, their spectroscopic behavior, and finally the properties arising from the assembly. We then move from molecules to more complex systems such as zeolite L nano-objects that can be used as nanocontainers and functionalized in different ways. We show how it is possible to organize rods of micron length in a geometrically controlled manner in solution and on surfaces. The assemblies are built by coordinative bonds and are luminescent materials that can be constructed from fluorescent building blocks, with potential applications as optoelectronic materials, in analogy to their molecular counterparts.

scholarly journals Self-Assembly in Materials Synthesis

MRS Bulletin ◽  
2005 ◽  
Vol 30 (10) ◽  
pp. 700-704 ◽  
Author(s):  
Matthew V. Tirrell ◽  
Alexander Katz
Keyword(s):  
Block Copolymers ◽  
Self Assembly ◽  
Molecular Crystals ◽  
Building Blocks ◽  
Materials Synthesis ◽  
Length Scales ◽  
Organic Molecular Crystals ◽  
Introductory Article ◽  
Small Building ◽  
Synthesis Of Materials

AbstractThe synthesis of materials via self-assembly typically involves the spontaneous and reversible organization of small building blocks for the purpose of creating conglomerate structures over larger length scales. This introductory article describes self-assembly processes on several length scales, from subnanometer up to millimeter scales, and briefly summarizes some of the incredible diversity of materials that exhibit selfassembly. Articles in this issue cover self-assembly using zeolitic structures, organic molecular crystals, block copolymers, surfactants, mesoscale templates, and soluble crystallization additives. Keywords: block copolymers, materials synthesis, self-assembly, surfactants, templates, zeolites.

Biomimetic materials: An introduction

1992 ◽  
Vol 50 (2) ◽  
pp. 1020-1021 ◽  
Author(s):  
M. Sarikaya ◽  
J. T. Staley ◽  
I. A. Aksay
Keyword(s):  
Self Assembly ◽  
Structural Control ◽  
Hierarchical Structures ◽  
Ceramic Composites ◽  
Advanced Materials ◽  
Length Scale ◽  
Spider Webs ◽  
Biomimetic Materials ◽  
Synthetic Materials ◽  
All Ceramic

Biomimetics is an area of research in which the analysis of structures and functions of natural materials provide a source of inspiration for design and processing concepts for novel synthetic materials. Through biomimetics, it may be possible to establish structural control on a continuous length scale, resulting in superior structures able to withstand the requirements placed upon advanced materials. It is well recognized that biological systems efficiently produce complex and hierarchical structures on the molecular, micrometer, and macro scales with unique properties, and with greater structural control than is possible with synthetic materials. The dynamism of these systems allows the collection and transport of constituents; the nucleation, configuration, and growth of new structures by self-assembly; and the repair and replacement of old and damaged components. These materials include all-organic components such as spider webs and insect cuticles (Fig. 1); inorganic-organic composites, such as seashells (Fig. 2) and bones; all-ceramic composites, such as sea urchin teeth, spines, and other skeletal units (Fig. 3); and inorganic ultrafine magnetic and semiconducting particles produced by bacteria and algae, respectively (Fig. 4).

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.

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