Kinetic Controlled Chirality Transfer and Induction in 2D Hydrogen-Bonding Assemblies of Glycylglycine on Au(111)

Chirality transfer is of vital importance that dominates the structure and functionality of biological systems and living matters. External physical stimulations, e.g. polarized light and mechanical forces, can trigger the chirality symmetry breaking, leading to the appearance of the enantiomeric entities created from a chiral self-assembly of achiral molecule. Here, several 2D assemblies with different chirality, synthesized on Au(111) surface by using achiral building blocks – glycylglycine (digly), the simplest polypeptide are reported. By delicately tuning the kinetic factors, i.e., one-step slow/rapid deposition, or stepwise slow deposition with mild annealing, achiral square hydrogen-bond organic frameworks (HOF), homochiral rhombic HOF and racemic rectangular assembly are achieved, respectively. Chirality induction and related symmetry broken in assemblies are introduced by the handedness (H-bond configurations in principle) of the assembled motifs and then amplified to the entire assemblies via the interaction between motifs. The results show that the chirality transfer and induction of biological assemblies can be tuned by altering the kinetic factors instead of applying external forces, which may offer an in-depth understanding and practical approach to peptide chiral assembly on the surfaces and can further facilitate the design of desired complex biomolecular superstructures.     

Protein folding and misfolding: a paradigm of self-assembly and regulation in complex biological systems

Understanding biological complexity is one of the grand scientific challenges for the future. A living organism is a highly evolved system made up of a large number of interwoven molecular networks. These networks primarily involve proteins, the macromolecules that enable and control virtually every chemical process that takes place in the cell. Proteins are also key elements in the essential characteristic of living systems, their ability to function and replicate themselves through controlled molecular interactions. Recent progress in understanding the most fundamental aspect of polypeptide self-organization, the process by which proteins fold to attain their active conformations, provides a global platform to gain knowledge about the function of biological systems and the regulatory mechanisms that underpin their ability to adapt to changing conditions. In order to exploit such progress effectively, we are developing a variety of approaches, including procedures that use experimental data to restrain the properties of complex systems in computer simulations, to describe their behaviour under a wide variety of conditions. We believe that such approaches can lead to significant advances in understanding biological complexity, in general, and protein folding and misfolding in particular. These advances would contribute to: a more effective exploitation of the information from genome sequences; more rational therapeutic approaches to diseases, particularly those associated with ageing; the responsible control of our own evolution; and the development of new technologies based on mimicking the principles of biological self-assembly, for instance in nanotechnology. More fundamentally, we believe that this research will result in a more coherent understanding of the origin, evolution and functional properties of living systems.     

Liquid crystal order in colloidal suspensions of spheroidal particles by direct current electric field assembly

DC electric fields are used to produce colloidal assemblies with orientational and layered positional order from a dilute suspension of spheroidal particles. These 3D assemblies, which can be visualized in situ by confocal microscopy, are achieved in short time spans (t < 1 h) by the application of a constant voltage across the capacitor-like device. This method yields denser and more ordered assemblies than had been previously reported with other assembly methods. Structures with a high degree of orientational order as well as layered positional order normal to the electrode surface are observed. These colloidal structures are explained as a consequence of electrophoretic deposition and field-assisted assembly. The interplay between the deposition rate and the rotational Brownian motion is found to be critical for the optimal ordering, which occurs when these rates, as quantified by the Peclet number, are of order one. The results suggest that the mechanism leading to ordering is equilibrium self-assembly but with kinetics dramatically accelerated by the application of the DC electric field. Finally, the crystalline symmetry of the densest structure formed is determined and compared with previously studied spheroidal assemblies.     

Stimuli-responsive polypeptide vesicles by conformation-specific assembly

In biology, lipids are well known for their ability to assemble into spherical vesicles. Proteins, in particular virus capsids, can also form regular vesicle-like structures, where the precise folding and stable conformations of many identical subunits directs their self-assembly. Functionality present on these subunits also controls their disassembly within the cellular environment, for example, in response to a pH change. Here, we report the preparation of diblock copolypeptides that self-assemble into spherical vesicular assemblies whose size and structure are dictated primarily by the ordered conformations of the polymer segments, in a manner similar to viral capsid assembly. Furthermore, functionality was incorporated into these molecules to render them susceptible to environmental stimuli, which is desirable for drug-delivery applications. The control of assembly and function exhibited in these systems is a significant advance towards the synthesis of materials that can mimic the precise three-dimensional assembly found in proteins.     

Relative positioning of toleranced polyhedral parts in an assembly

Parts with geometric (size and shape) variations generate uncertainties in every assembly configuration. The resultant uncertain assemblies are far more complicated than the nominal assembly configurations. To perform tolerance analysis, the real positions of variant parts in a variant assembly configuration need to be investigated. In this paper, a relative positioning scheme is proposed to determine the optimal configuration of variant parts in an assembly. A method of calculating and representing positions of 3D polyhedral parts in assembly has been presented. Translational and rotational constraints, which are developed corresponding to the extra degrees of freedom caused by the shape and size variation of parts, have been formulated. By computing translational and rotational constraints, the allowed motion space for each mating pair is obtained. Assembly configuration uncertainties caused by part variations are clarified by realizing the transformation of the object part according to the objective function, A 3D example is given to explain how the proposed relative positioning scheme is used in tolerance analysis of assemblies.     

Devising Synthetic Reaction Cycles for Dissipative Nonequilibrium Self-Assembly

Fuel-driven reaction cycles are found in biological systems to control the assembly and disassembly of supramolecular materials such as the cytoskeleton. Fuel molecules can bind noncovalently to a self-assembling building block or they can react with it, resulting in covalent modifications. Overall the fuel can either switch the self-assembly process on or off. Here, a closer look is taken at artificial systems that mimic biological systems by making and breaking covalent bonds in a self-assembling motif. The different chemistries used so far are highlighted in chronological order and the pros and cons of each system are discussed. Moreover, the desired traits of future reaction cycles, their fuels, and waste management are outlined, and two chemistries that have not been explored up to now in chemically fueled dissipative self-assembly are suggested.     

Paradigm shift from self-assembly to commanded assembly of functional materials: recent examples in porphyrin/fullerene supramolecular systems

Abstract

Current nanotechnology based on top-down nanofabrication may encounter a variety of drawbacks in the near future so that development of alternative methods, including the so-called bottom-up approach, has attracted considerable attention. However, the bottom-up strategy, which often relies on spontaneous self-assembly, might be inefficient in the development of the requisite functional materials and systems. Therefore, assembly processes controlled by external stimuli might be a plausible strategy for the development of bottom-up nanotechnology. In this review, we demonstrate a paradigm shift from self-assembly to commanded assembly by describing several examples of assemblies of typical functional molecules, i.e. porphyrins and fullerenes. In the first section, we describe recent progress in the design and study of self-assembled and co-assembled supramolecular architectures of porphyrins and fullerenes. Then, we show examples of assembly induced by external stimuli. We emphasize the paradigm shift from self-assembly to commanded assembly by describing the recently developed electrochemical-coupling layer-by-layer (ECC-LbL) methodology.     

"Chemical transformers" from nanoparticle ensembles operated with logic

The pH-responsive nanoparticles were coupled with information-processing enzyme-based systems to yield "smart" signal-responsive hybrid systems with built-in Boolean logic. The enzyme systems performed AND/OR logic operations, transducing biochemical input signals into reversible structural changes (signal-directed self-assembly) of the nanoparticle assemblies, thus resulting in the processing and amplification of the biochemical signals. The hybrid system mimics biological systems in effective processing of complex biochemical information, resulting in reversible changes of the self-assembled structures of the nanoparticles. The bioinspired approach to the nanostructured morphing materials could be used in future self-assembled molecular robotic systems.     

Nanoscale transport enables active self-assembly of millimeter-scale wires

Active self-assembly processes exploit an energy source to accelerate the movement of building blocks and intermediate structures and modify their interactions. A model system is the assembly of biotinylated microtubules partially coated with streptavidin into linear bundles as they glide on a surface coated with kinesin motor proteins. By tuning the assembly conditions, microtubule bundles with near millimeter length are created, demonstrating that active self-assembly is beneficial if components are too large for diffusive self-assembly but too small for robotic assembly.     

Self-organization: making complex infectious viral particles from purified precursors

Viruses have served as excellent model systems in which to study biological self-organization. Purified virion structural constituents have been shown to self-assemble into particles that can initiate a productive infection in the host cell resulting in the release of progeny virions. Accumulating information on virus structures and assembly principles has revealed unexpected similarities between viruses that infect hosts as diverse as bacteria and humans, suggesting that these viruses had an early common ancestor. I will describe, in more detail, the assembly pathway of a complex double-stranded RNA bacterial virus. In this system, infectious viral particles are produced starting from purified protein and nucleic acid constituents through an elaborate self-assembly, RNA-packaging and synthesis pathway.     

Colloid chemical approach to nanoelectrode ensembles with highly controllable active area fraction

A novel "bottom-up" approach to highly controllable nanoelectrode ensembles (NEEs) has been developed using colloidal nanoparticle self-assembly techniques. This solution-based strategy allows flexible control over nanoelectrode size, shape, and interspacing of the as-prepared NEEs. Atomic force microscopy (AFM) was proved to be a powerful tool to monitor the NEE topography, which yields parameters that can be used to calculate the fractional nanoelectrode area of the NEEs. AFM, ac impedance, and cyclic voltammetry studies demonstrate that most of nanoelectrodes on the NEEs (at least by 9-min self-assembly) are not diffusionally isolated under conventional ac frequency range and scan rates. As a result, the NEEs behave as "nanoelectrode-patch" assemblies. Besides, the as-prepared NEEs by different self-assembling times show an adjustable sensitivity to heterogeneous electron-transfer kinetics, which may be helpful to sensor applications. Like these NEEs constructed by other techniques, the present NEEs prepared by chemical self-assembly also exhibit the enhancement of electroanalytical detection limit consistent with NEE theory prediction.     

Dynamic Self‐Assembly of Homogenous Microcyclic Structures Controlled by a Silver‐Coated Nanopore

The self‐assembly of nanoparticles is a challenging process for organizing precise structures with complicated and ingenious structures. In the past decades, a simple, high‐efficiency, and reproducible self‐assembly method from nanoscale to microscale has been pursued because of the promising and extensive application prospects in bioanalysis, catalysis, photonics, and energy storage. However, microscale self‐assembly still faces big challenges including improving the stability and homogeneity as well as pursuing new assembly methods and templates for the uniform self‐assembly. To address these obstacles, here, a novel silver‐coated nanopore is developed which serves as a template for electrochemically generating microcyclic structures of gold nanoparticles at micrometers with highly homogenous size and remarkable reproducibility. Nanopore‐induced microcyclic structures are further applied to visualize the diffusion profile of ionic flux. Based on this novel strategy, a nanopore could potentially facilitate the delivery of assembled structures for many practical applications including drug delivery, cellular detection, catalysis, and plasmonic sensing.     

Systematic Engineering of Uniform,Highly Efficient,Targeted and Shielded Viral‐Mimetic Nanoparticles

In the past decades, numerous types of nanomedicines have been developed for the efficient and safe delivery of nucleic acid‐based drugs for cancer therapy. Given that the destination sites for nucleic acid‐based drugs are inside cancer cells, delivery systems need to be both targeted and shielded in order to overcome the extracellular and intracellular barriers. One of the major obstacles that has hindered the translation of nanotechnology‐based gene‐delivery systems into the clinic has been the complexity of the design and assembly processes, resulting in non‐uniform nanocarriers with unpredictable surface properties and efficiencies. Consequently, no product has reached the clinic yet. In order to address this shortcoming, a multifunctional targeted biopolymer is genetically engineered in one step, eliminating the need for multiple chemical conjugations. Then, by systematic modulation of the ratios of the targeted recombinant vector to PEGylated peptides of different sizes, a library of targeted–shielded viral‐mimetic nanoparticles (VMNs) with diverse surface properties are assembled. Through the use of physicochemical and biological assays, targeted–shielded VMNs with remarkably high transfection efficiencies (>95%) are screened. In addition, the batch‐to‐batch variability of the assembled targeted–shielded VMNs in terms of uniformity and efficiency is examined and, in both cases, the coefficient of variation is calculated to be below 20%, indicating a highly reproducible and uniform system. These results provide design parameters for engineering uniform, targeted–shielded VMNs with very high cell transfection rates that exhibit the important characteristics for in vivo translation. These design parameters and principles could be used to tailor‐make and assemble targeted–shielded VMNs that could deliver any nucleic acid payload to any mammalian cell type.     

Electrostatic and capillary force directed tunable 3D binary micro- and nanoparticle assemblies on surfaces

We report a simple, rapid and cost-effective method based on evaporation induced assembly to grow 3D binary colloidal assemblies on a hydrophobic/hydrophilic substrate by simple drop casting. The evaporation of a mixed colloidal drop results in ring-like or uniform area deposition depending on the concentration of particles, and thus assembly occurs at the periphery of a ring or uniformly all over the drop area. Binary colloidal assemblies of different crystal structure are successfully prepared over a wide range of size ratios (γ = small/large) from 0.06 to 0.30 by tuning the γ of the micro- and nanoparticles used during assembly. The growth mechanism of 3D binary colloidal assemblies is investigated and it is found that electrostatic forces facilitate assembly formation until the end of the evaporation process, with capillary forces also playing a role. In addition, the effects of solvent type, humidity, and salt concentration on crystal formation and ordering behaviour are also examined. Furthermore, long range, highly ordered binary colloidal assemblies can be fabricated by the choice of a low conducting solvent combined with evaporation induced assembly.     

层层自组装技术的研究进展及应用情况

层层自组装技术(Layer-by-layer self-assembly,LbL)是正处于发展阶段的新技术。与传统成膜技术相比,该技术能组装的材料多种多样(如聚电解质、纳米颗粒、有机小分子等),可以通过模板精确控制薄膜的表面结构和尺寸。薄膜的通透性能和力学性能可以通过控制组装材料、沉积层数、组装条件等来改善。对层层自组装技术的研究进展及应用情况进行了综述,较为详细地介绍了层与层之间作用力的研究进展,阐述了LbL技术在电化学电容器、光敏微胶囊、分离膜、生物化学及药物释放中的应用,并对LbL技术的发展前景进行了展望     

Supramolecular Energy Materials

Self-assembly is a bioinspired strategy to craft materials for renewable and clean energy technologies. In plants, the alignment and assembly of the light-harvesting protein machinery in the green leaf optimize the ability to efficiently convert light from the sun to form chemical bonds. In artificial systems, strategies based on self-assembly using noncovalent interactions offer the possibility to mimic this functional correlation among molecules to optimize photocatalysis, photovoltaics, and energy storage. One of the long-term objectives of the field described here as supramolecular energy materials is to learn how to design soft materials containing light-harvesting assemblies and catalysts to generate fuels and useful chemicals. Supramolecular energy materials also hold great potential in the design of systems for photovoltaics in which intermolecular interactions in self-assembled structures, for example, in electron donor and acceptor phases, maximize charge transport and avoid exciton recombination. Possible pathways to integrate organic and inorganic structures by templating strategies and electrodeposition to create materials relevant to energy challenges including photoconductors and supercapacitors are also described. The final topic discussed is the synthesis of hybrid perovskites in which organic molecules are used to modify both structure and functions, which may include chemical stability, photovoltaics, and light emission.     

Modular Molecular Self‐Assembly for Diversified Chiroptical Systems

Bottom‐up multicomponent molecular self‐assembly is an efficient approach to fabricate and manipulate chiral nanostructures and their chiroptical activities such as the Cotton effect and circular polarized luminescence (CPL). However, the integrated coassembly suffers from spontaneous and inherent systematic pathway complexity with low yield and poor fidelity. Consequently, a rational design of chiral self‐assembled systems with more than two components remains a significant challenge. Herein, a modularized, ternary molecular self‐assembly strategy that generates chiroptically active materials at diverse hierarchical levels is reported. N‐terminated aromatic amino acids appended with binding sites for charge transfer and multiple hydrogen bonds undergo the evolution of supramolecular chirality with unique handedness and luminescent color, generating abundant CPL emission with high luminescence dissymmetry factor values in precisely controlled modalities. Ternary coassembly facilitates high‐water‐content hydrogel formation constituted by super‐helical nanostructures, demonstrating a helix to toroid topological transition. This discovery would shed light on developing complicated multicomponent systems in mimicking biological coassembly events.     

Computational modelling of manufacturing choice complexity in a mixed-model assembly line

Manufacturing systems have evolved to adopt a mixed-model assembly line enabling the production of high product variety. Although the mixed-model assembly system with semi-automation (i.e. human involvement) can offer a wide range of advantages, the system becomes very complex as variety increases. Further, while the complexity from different options can worsen the system performance, there is a lack of quantifiable models for manufacturing complexity in the literature. Thus, in this paper, we propose a novel method to quantify manufacturing choice complexity for the effective management of semi-automated systems in a mixed-model assembly line. Based on the concept of information entropy, our model considers both the options mix and the similarities between options. The proposed model, along with an illustrative case study, not only serves as a tool to quantitatively assess the impact of choice complexity on total system performance, but also provides an insight into how complexity can be mitigated without affecting the overall manufacturing throughput.     

Assembling of dense fluorescent supramolecular webs via self-propelled star-shaped aggregates

We report a novel mechanism of assembly of dendronized rod molecules into a dense supramolecular fluorescencent web featuring self-propelled mechanistic inward motion of star-shaped aggregates within a solution droplet. We suggest that such a motion (observed in real time) is caused by the self-repulsion of the growing star-shaped nuclei from the liquid-solid-air interface in the course of one-dimensional growth of the anchored arms. An intriguing mechanism discovered here involves microscopic (hundred micrometers) directional motion of the microscopic aggregates driven by one-dimensional molecular assembly, which opens a new venue for guided assembly of dense mesoscopic supramolecular webs. Such assemblies can serve as interesting microfluidic networks, a web of optical switches, and model systems for studying intercellular communication.