scholarly journals Predictive Self-Assembly of Complex Crystals via Building Block Design

2014 ◽  
Vol 70 (a1) ◽  
pp. C1537-C1537
Author(s):  
Pablo Damasceno ◽  
Michael Engel ◽  
Sharon Glotzer

A primary challenge for the development of bulk, scalable, and high yield materials with interesting properties is the limited number of structures that can be obtained via self-assembly of nano and micrometer sized particles. Systematic and extensive computational studies of hard polyhedral particles have demonstrated that anisotropy of the building blocks can be a viable route for increasing variability of assembled patterns [1, 2, 3]. Interestingly, the types of structures assembled from this method were shown to be predictable from information contained already in the dense fluid, prior to crystallization. In this talk, the role of such local structures for self-assembly will be rationalized and we will demonstrate how this information can be used as a strategy for design of crystalline and quasicrystalline patterns for both symmetric and asymmetric particles.

Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1502
Author(s):  
Johannes M. Parikka ◽  
Karolina Sokołowska ◽  
Nemanja Markešević ◽  
J. Jussi Toppari

The predictable nature of deoxyribonucleic acid (DNA) interactions enables assembly of DNA into almost any arbitrary shape with programmable features of nanometer precision. The recent progress of DNA nanotechnology has allowed production of an even wider gamut of possible shapes with high-yield and error-free assembly processes. Most of these structures are, however, limited in size to a nanometer scale. To overcome this limitation, a plethora of studies has been carried out to form larger structures using DNA assemblies as building blocks or tiles. Therefore, DNA tiles have become one of the most widely used building blocks for engineering large, intricate structures with nanometer precision. To create even larger assemblies with highly organized patterns, scientists have developed a variety of structural design principles and assembly methods. This review first summarizes currently available DNA tile toolboxes and the basic principles of lattice formation and hierarchical self-assembly using DNA tiles. Special emphasis is given to the forces involved in the assembly process in liquid-liquid and at solid-liquid interfaces, and how to master them to reach the optimum balance between the involved interactions for successful self-assembly. In addition, we focus on the recent approaches that have shown great potential for the controlled immobilization and positioning of DNA nanostructures on different surfaces. The ability to position DNA objects in a controllable manner on technologically relevant surfaces is one step forward towards the integration of DNA-based materials into nanoelectronic and sensor devices.


Author(s):  
Rakesh Murthy ◽  
Aditya N. Das ◽  
Dan O. Popa

Heterogeneous assembly at the microscale has recently emerged as a viable pathway to constructing 3-dimensional microrobots and other miniaturized devices. In contrast to self-assembly, this method is directed and deterministic, and is based on serial or parallel microassembly. Whereas at the meso and macro scales, automation is often undertaken after, and often benchmarked against manual assembly, we demonstrate that deterministic automation at the MEMS scale can be completed with higher yields through the use of engineered compliance and precision robotic cells. Snap fasteners have long been used as a way to exploit the inherent stability of local minima of the deformation energy caused by interference during part mating. In this paper we assume that the building blocks are 2 1/2 -dimensional, as is the case with lithographically microfabricated MEMS parts. The assembly of the snap fasteners is done using μ3, a multi-robot microassembly station with unique characteristics located at our ARRI’s Texas Microfactory lab. Experiments are performed to demonstrate that fast and reliable assemblies can be expected if the microparts and the robotic cell satisfy a so-called “High Yield Assembly Condition” (H.Y.A.C.). Important design trade-offs for assembly and performance of microsnap fasteners are discussed and experimentally evaluated.


2016 ◽  
Vol 7 ◽  
pp. 613-629 ◽  
Author(s):  
Claudia Koch ◽  
Fabian J Eber ◽  
Carlos Azucena ◽  
Alexander Förste ◽  
Stefan Walheim ◽  
...  

The rod-shaped nanoparticles of the widespread plant pathogentobacco mosaic virus(TMV) have been a matter of intense debates and cutting-edge research for more than a hundred years. During the late 19th century, their behavior in filtration tests applied to the agent causing the 'plant mosaic disease' eventually led to the discrimination of viruses from bacteria. Thereafter, they promoted the development of biophysical cornerstone techniques such as electron microscopy and ultracentrifugation. Since the 1950s, the robust, helically arranged nucleoprotein complexes consisting of a single RNA and more than 2100 identical coat protein subunits have enabled molecular studies which have pioneered the understanding of viral replication and self-assembly, and elucidated major aspects of virus–host interplay, which can lead to agronomically relevant diseases. However, during the last decades, TMV has acquired a new reputation as a well-defined high-yield nanotemplate with multivalent protein surfaces, allowing for an ordered high-density presentation of multiple active molecules or synthetic compounds. Amino acid side chains exposed on the viral coat may be tailored genetically or biochemically to meet the demands for selective conjugation reactions, or to directly engineer novel functionality on TMV-derived nanosticks. The natural TMV size (length: 300 nm) in combination with functional ligands such as peptides, enzymes, dyes, drugs or inorganic materials is advantageous for applications ranging from biomedical imaging and therapy approaches over surface enlargement of battery electrodes to the immobilization of enzymes. TMV building blocks are also amenable to external control of in vitro assembly and re-organization into technically expedient new shapes or arrays, which bears a unique potential for the development of 'smart' functional 3D structures. Among those, materials designed for enzyme-based biodetection layouts, which are routinely applied, e.g., for monitoring blood sugar concentrations, might profit particularly from the presence of TMV rods: Their surfaces were recently shown to stabilize enzymatic activities upon repeated consecutive uses and over several weeks. This review gives the reader a ride through strikingly diverse achievements obtained with TMV-based particles, compares them to the progress with related viruses, and focuses on latest results revealing special advantages for enzyme-based biosensing formats, which might be of high interest for diagnostics employing 'systems-on-a-chip'.


mBio ◽  
2019 ◽  
Vol 10 (6) ◽  
Author(s):  
K. M. Cosert ◽  
Angelines Castro-Forero ◽  
Rebecca J. Steidl ◽  
Robert M. Worden ◽  
G. Reguera

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.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Francesco Serafin ◽  
Jun Lu ◽  
Nicholas Kotov ◽  
Kai Sun ◽  
Xiaoming Mao

AbstractSelf-organized complex structures in nature, e.g., viral capsids, hierarchical biopolymers, and bacterial flagella, offer efficiency, adaptability, robustness, and multi-functionality. Can we program the self-assembly of three-dimensional (3D) complex structures using simple building blocks, and reach similar or higher level of sophistication in engineered materials? Here we present an analytic theory for the self-assembly of polyhedral nanoparticles (NPs) based on their crystal structures in non-Euclidean space. We show that the unavoidable geometrical frustration of these particle shapes, combined with competing attractive and repulsive interparticle interactions, lead to controllable self-assembly of structures of complex order. Applying this theory to tetrahedral NPs, we find high-yield and enantiopure self-assembly of helicoidal ribbons, exhibiting qualitative agreement with experimental observations. We expect that this theory will offer a general framework for the self-assembly of simple polyhedral building blocks into rich complex morphologies with new material capabilities such as tunable optical activity, essential for multiple emerging technologies.


2019 ◽  
Vol 48 (27) ◽  
pp. 10260-10274 ◽  
Author(s):  
Tatiana R. G. Simões ◽  
Maria Vanda Marinho ◽  
Jorge Pasán ◽  
Humberto O. Stumpf ◽  
Nicolás Moliner ◽  
...  

Herein we present the self-assembly of the [Cu(opba)]2− and [Cu(dmphen)]2+ building blocks in the presence of thiocyanate (1), chloride (2), bromide (3) and dicyanamide (4) anions.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Alexander E. S. Van Driessche ◽  
Nani Van Gerven ◽  
Rick R. M. Joosten ◽  
Wai Li Ling ◽  
Maria Bacia ◽  
...  

AbstractSelf-assembly of proteins holds great promise for the bottom-up design and production of synthetic biomaterials. In conventional approaches, designer proteins are pre-programmed with specific recognition sites that drive the association process towards a desired organized state. Although proven effective, this approach poses restrictions on the complexity and material properties of the end-state. An alternative, hierarchical approach that has found wide adoption for inorganic systems, relies on the production of crystalline nanoparticles that become the building blocks of a next-level assembly process driven by oriented attachment (OA). As it stands, OA has not yet been observed for protein systems. Here we employ cryo-transmission electron microscopy (cryoEM) in the high nucleation rate limit of protein crystals and map the self-assembly route at molecular resolution. We observe the initial formation of facetted nanocrystals that merge lattices by means of OA alignment well before contact is made, satisfying non-trivial symmetry rules in the process. As these nanocrystalline assemblies grow larger we witness imperfect docking events leading to oriented aggregation into mesocrystalline assemblies. These observations highlight the underappreciated role of the interaction between crystalline nuclei, and the impact of OA on the crystallization process of proteins.


2020 ◽  
Vol 2 (2) ◽  
pp. 17

Aqueous self-assembly customarily focuses on the molecular interactions of assembling building blocks; the role of water is barely studied. The hydration of hydrophobic P+X- (P+: macromolecular phosphonium cation, X-: anion) is dependent on the ionic end groups, which is responsible for the consequent assembling behavior. The water interaction with the backbone was analyzed by FT-IR, and the dynamics were measured by low field-NMR spectroscopy. The combination of these two techniques reveals the effect of X- on hydration. When X- is I-, the ionic end group ordered water molecules that exerted a detectable long-range effect de-hydrating the backbone. The consequent hydrophobic interaction drove the aqueous assembly of P+I- into micelle-like aggregates with the ionic group exposed to water. In contrast, the ion pair with a hydrophobic anion of [BPh4]- was not able to hold water and did not deplete the hydration water. The hydrated backbone of P+[BPh4]- assembled into vesicles that were driven by hydration interactions. This elucidation at the molecular level is craved to progress aqueous supramolecular chemistry.


Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1553 ◽  
Author(s):  
Marina Sokolsky-Papkov ◽  
Alexander Kabanov

Synthesis of gold nanoparticles (GNP) by reacting chloroauric acid (HAuCl4) and Pluronic F127 was thoroughly investigated. The rate of reduction of HAuCl4 and the yield and morphology of GNP strongly depended on the concentration of the reactants and sodium chloride, as well as pH and temperature. Upon completion of the reaction heterogeneous mixtures of small GNP of defined shape and Pluronic aggregates were formed. GNP were separated from the excess of Pluronic by centrifugal filtration. Under optimized conditions the GNP were small (ca. 80 nm), uniform (PDI ~0.09), strongly negatively charged (ζ-potential −30 mV) and nearly spherical. They were stable in distilled water and phosphate-buffered saline. Purified GNP contained ~13% by weight of an organic component, yet presence of polypropylene oxide was not detected suggesting that Pluronic was not adsorbed on their surface. Analysis of the soluble products suggested that the copolymer undergoes partial degradation accompanied by cleavage of the C–O bonds and appearance of new primary hydroxyl groups. The reaction involves formation of free radicals and hydroperoxides depends on the oxygen concentration. GNP did not form at 4 °C when the micellization of Pluronic was abolished reinforcing the role of the copolymer self-assembly. In conclusion, this work provides insight into the mechanism of HAuCl4 reduction and GNP formation in the presence of Pluronic block copolymers. It is useful for improving the methods of manufacturing uniform and pure GNP that are needed as nanoscale building blocks in nanomedicine applications.


2004 ◽  
Vol 76 (7-8) ◽  
pp. 1365-1374 ◽  
Author(s):  
L. M. Croll ◽  
H. D. H. Stöver

Poly(divinylbenzene-55)[poly(DVB-55] microspheres were used as building blocks to form polymer capsule walls consisting of interconnected microspheres. The microspheres had to be surface-functionalized with maleic acid to facilitate their interfacial assembly. In addition, porous and functionalized poly(DVB-55) microspheres were embedded across interfacial polyurea capsule membranes to form composite tectocapsules where release of core materials is designed to occur through the microsphere pores, rather than by conventional wall diffusion. Electron microscopy and X-ray spectromicroscopy were used to characterize the wall compositions, and release data are presented to illustrate the role of microspheres acting as release portals.


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