Self-assembly of cellulose for creating green materials with tailor-made nanostructures

Author(s):  
Yuuki Hata ◽  
Takeshi Serizawa

Inspired by living systems, biomolecules have been employed in vitro as building blocks for creating advanced nanostructured materials. In regard to nucleic acids, peptides, and lipids, their self-assembly pathways and...

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'.


2018 ◽  
Vol 56 (5) ◽  
Author(s):  
Trung Dac Nguyen ◽  
Hanh Thi Hong Nguyen ◽  
Minh Duy Le ◽  
Hung Xuan Truong

Next-generation nanotechnology demands new materials and devices that are highly efficient, multifunctional, cost-effective and environmental friendly. The need to accelerate the discovery of new materials therefore becomes more pressing than ever. Over the past two decades, self-assembly techniques have provided a promising means for fabricating nanomaterials, where the underlying structures are formed by the self-organization of building blocks, such as nanoparticles, colloids and block copolymers, in a similar fashion to biological systems. The fundamental challenges to these bottom techniques are to design suitable assembling units, to tailor their interaction rules and to identify possible assembly pathways. In this report, we will demonstrate how computer simulation has been a powerful tool for tackling these fundamental challenges, providing not only profound insights into the complex interplay between the building blocks’ geometry and their interactions, but also valuable predictions to inspire on-going and future experiment. Theoretical background of self-assembly studies; simulation methods and data analysis tools commonly used will also be discussed.


Author(s):  
Ahyoung Kim ◽  
Lehan Yao ◽  
Falon Kalutantirige ◽  
Shan Zhou ◽  
Qian Chen

Biological building blocks (i.e., proteins) are encoded with the information of target structure into the chemical and morphological patches, guiding their assembly into the levels of functional structures that are crucial for living organisms. Learning from nature, researchers have been attracted to the artificial analogues, “patchy particles,” which have controlled geometries of patches that serve as directional bonding sites. However, unlike the abundant studies of micron-scale patchy particles, which demonstrated complex assembly structures and unique behaviors attributed to the patches, research on patchy nanoparticles (NPs) has remained challenging. In the present chapter, we discuss the recent understandings on patchy NP design and synthesis strategies, and physical principles of their assembly behaviors, which are the main factors to program patchy NP self-assembly into target structures that cannot be achieved by conventional non-patched NPs. We further summarize the self-assembly of patchy NPs under external fields, in simulation, and in kinetically controlled assembly pathways, to show the structural richness patchy NPs bring. The patchy NP assembly is novel by their structures as well as the multicomponent features, and thus exhibits unique optical, chemical, and mechanical properties, potentially aiding applications in catalysts, photonic crystals, and metamaterials as well as fundamental nanoscience.


2019 ◽  
Vol 2 (1) ◽  
Author(s):  
Leonardo Hayato Foianesi-Takeshige ◽  
Satoshi Takahashi ◽  
Tomoki Tateishi ◽  
Ryosuke Sekine ◽  
Atsushi Okazawa ◽  
...  

Abstract The template effect is a key feature to control the arrangement of building blocks in assemblies, but its kinetic nature remains elusive compared to the thermodynamic aspects, with the exception of very simple reactions. Here we report a kinetic template effect in a self-assembled cage composed of flexible ditopic ligands and Pd(II) ions. Without template anion, a micrometer-sized sheet is kinetically trapped (off-pathway), which is converted into the thermodynamically most stable cage by the template anion. When the template anion is present from the start, the cage is selectively produced by the preferential cyclization of a dinuclear intermediate (on-pathway). Quantitative and numerical analyses of the self-assembly of the cage on the on-pathway revealed that the accelerating effect of the template is stronger for the early stage reactions of the self-assembly than for the final cage formation step itself, indicating the kinetic template effect.


eLife ◽  
2014 ◽  
Vol 3 ◽  
Author(s):  
Yann Gambin ◽  
Nicholas Ariotti ◽  
Kerrie-Ann McMahon ◽  
Michele Bastiani ◽  
Emma Sierecki ◽  
...  

In mammalian cells three closely related cavin proteins cooperate with the scaffolding protein caveolin to form membrane invaginations known as caveolae. Here we have developed a novel single-molecule fluorescence approach to directly observe interactions and stoichiometries in protein complexes from cell extracts and from in vitro synthesized components. We show that up to 50 cavins associate on a caveola. However, rather than forming a single coat complex containing the three cavin family members, single-molecule analysis reveals an exquisite specificity of interactions between cavin1, cavin2 and cavin3. Changes in membrane tension can flatten the caveolae, causing the release of the cavin coat and its disassembly into separate cavin1-cavin2 and cavin1-cavin3 subcomplexes. Each of these subcomplexes contain 9 ± 2 cavin molecules and appear to be the building blocks of the caveolar coat. High resolution immunoelectron microscopy suggests a remarkable nanoscale organization of these separate subcomplexes, forming individual striations on the surface of caveolae.


Science ◽  
2013 ◽  
Vol 341 (6150) ◽  
pp. 1089-1094 ◽  
Author(s):  
Mark C. Walker ◽  
Benjamin W. Thuronyi ◽  
Louise K. Charkoudian ◽  
Brian Lowry ◽  
Chaitan Khosla ◽  
...  

Organofluorines represent a rapidly expanding proportion of molecules that are used in pharmaceuticals, diagnostics, agrochemicals, and materials. Despite the prevalence of fluorine in synthetic compounds, the known biological scope is limited to a single pathway that produces fluoroacetate. Here, we demonstrate that this pathway can be exploited as a source of fluorinated building blocks for introduction of fluorine into natural-product scaffolds. Specifically, we have constructed pathways involving two polyketide synthase systems, and we show that fluoroacetate can be used to incorporate fluorine into the polyketide backbone in vitro. We further show that fluorine can be inserted site-selectively and introduced into polyketide products in vivo. These results highlight the prospects for the production of complex fluorinated natural products using synthetic biology.


2017 ◽  
Vol 2017 ◽  
pp. 1-45 ◽  
Author(s):  
Janos Sagi

Synthetic analogs of natural nucleotides have long been utilized for structural studies of canonical and noncanonical nucleic acids, including the extensively investigated polymorphic G-quadruplexes (GQs). Dependence on the sequence and nucleotide modifications of the folding landscape of GQs has been reviewed by several recent studies. Here, an overview is compiled on the thermodynamic stability of the modified GQ folds and on how the stereochemical preferences of more than 70 synthetic and natural derivatives of nucleotides substituting for natural ones determine the stability as well as the conformation. Groups of nucleotide analogs only stabilize or only destabilize the GQ, while the majority of analogs alter the GQ stability in both ways. This depends on the preferredsynorantiN-glycosidic linkage of the modified building blocks, the position of substitution, and the folding architecture of the native GQ. Natural base lesions and epigenetic modifications of GQs explored so far also stabilize or destabilize the GQ assemblies. Learning the effect of synthetic nucleotide analogs on the stability of GQs can assist in engineering a required stable GQ topology, and exploring thein vitroaction of the single and clustered natural base damage on GQ architectures may provide indications for the cellular events.


2022 ◽  
Author(s):  
Ruiqi Liang ◽  
Yazhen Xue ◽  
Xiaowei Fu ◽  
An Le ◽  
Qingliang Song ◽  
...  

The inability to synthesize hierarchical structures with independently tailored nanoscale and mesoscale features limits the discovery of next-generation multifunctional materials. We present a programmable molecular self-assembly strategy to craft nanostructured materials with a variety of phase-in-phase hierarchical morphologies. The compositionally anisotropic building blocks employed in the assembly process are formed by multi-component graft block copolymers (GBCPs) containing sequence-defined side chains. The judicious design of various structural parameters in the GBCPs enables broadly tunable compositions, morphologies, and lattice parameters across the nanoscale and mesoscale in the assembled structures. Our strategy introduces new design principles for the efficient creation of complex hierarchical structures and provides a facile synthetic platform to access nanomaterials with multiple precisely integrated functionalities.


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 22 (4) ◽  
pp. 2223
Author(s):  
Ruslan Kashapov ◽  
Lucia Zakharova

The current task of the molecular sciences is to create unique nanostructured materials with a given structure and with specific physicochemical properties on the basis of the existing wide range of molecules of natural and synthetic origin. A promising and inexpensive way to obtain nanostructured materials is the spontaneous self-assembly of molecular building blocks during random collisions in real dispersive systems in solution and at interfaces. This editorial aims to summarize the major points from the 11 scientific papers that contributed to the special issue “The Self-Assembly and Design of Polyfunctional Nanosystems”, assessing the modern self-assembly potential and strategies for maintaining sustainable development of the nanoindustry.


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