Self-assembly Mechanism Research Articles

Supramolecular Thixotropic Ionogel Electrolyte for Sodium Batteries.

Owing to the potential of sodium as an alternative to lithium as charge carrier, increasing attention has been focused on the development of high-performance electrolytes for Na batteries in recent years. In this regard, gel-type electrolytes, which combine the outstanding ionic conductivity of liquid electrolytes and the safety of solid electrolytes, demonstrate immense application prospects. However, most gel electrolytes not only need a number of specific techniques for molding, but also typically suffer from breakage, leading to a short service life and severe safety issues. In this study, a supramolecular thixotropic ionogel electrolyte is proposed to address these problems. This thixotropic electrolyte is formed by the supramolecular self-assembly of D-gluconic acetal-based gelator (B8) in an ionic liquid solution of a Na salt, which exhibits moldability, a high ionic conductivity, and a rapid self-healing property. The ionogel electrolyte is chemically stable to Na and exhibits a good Na+ transference number. In addition, the self-assembly mechanism of B8 and thixotropic mechanism of ionogel are investigated. The safe, low-cost and multifunctional ionogel electrolyte developed herein supports the development of future high-performance Na batteries.

Study on the self-assembly of aromatic antimicrobial peptides based on different PAF26 peptide sequences

Abstract Antimicrobial peptide (AMP) self-assembly is an effective way to synthesis antimicrobial biomaterials. In previous studies, we found PAF26 AMP (Ac-RKKWFW-NH2) and its derivative K2–F2 peptide (Ac-KKRKKWFWFF-NH2) could both self-assemble into hydrogels, but they had distinct microscopic structures. Therefore, in this work five PAF26 peptide derivatives with different numbers of aromatic amino acids are designed to better understand the self-assembly mechanism of aromatic AMP. The transmission electron microscopy, infrared spectroscopy, circular dichroism, and fluorescence spectroscopy characterizations are carried out to study the microscope structure, secondary conformation, and molecular interactions. It is found that the five peptide derivatives have different microscopic structures, and the number of aromatic amino acids will affect the peptide hydrogen bonding and aromatic stacking interactions, causing significant differences in the secondary conformation and microscopic structure. This work will enhance the comprehension of aromatic AMP self-assembly.

EFFECTS OF SURFACE LIGANDS ON THE FORMATION OF SPHERICAL HOLLOW NICKEL PHOSPHIDE NANOPARTICLES AND THEIR SELF-ASSEMBLIES

Nickel phosphide nanoparticles have been well known for their electrical, catalytic, and corrosion-resistant properties. In the synthesis of hollow nickel phosphide nanoparticles, the role of surface ligands was very important in forming hollow structures. Thus, in this article, we systematically investigated the effects of different ligands on the formation of spherical hollow nickel phosphide nanoparticles. Specifically, our results showed that when primary amines with long alkyl chains were used, spherical hollow nickel phosphide nanoparticles were obtained. On the other hand, when amines with bulky head groups, bulky alkyl chains, or ligands with different head groups were used, spherical hollow nickel phosphide nanoparticles did not form. Furthermore, moderate use of tri-n-octylphosphine (TOP), another surface ligand and P precursor, was also a contributing factor to the hollow nickel phosphide formation. Interestingly, we discovered that limited use of TOP induced self-assembling of spherical hollow nickel phosphide nanoparticles into micro-sized assemblies. The assemblies were spherical, compact and uniform, which further showing the use of surface ligands as a tool to engineer novel material structures from the nano-/micro-scales. We are currently directing our efforts toward more understanding of the self-assembling mechanism at the sub-nano scale as well as proposing possible application for our nanoparticles and their assemblies.

Static Scanning Tunneling Microscopy Images Reveal the Mechanism of Supramolecular Polymerization of an Oligopyridine on Graphite.

Supramolecular polymerization of a donor–acceptor bisterpyridine (BTP) equipped with an electron‐rich carbazole unit is observed by scanning tunneling microscopy (STM) at the highly oriented pyrolytic graphite (HOPG)|solution interface. It is shown that two‐dimensional crystals of supramolecular (co)polymers are formed by chain growth polymerization, which in turn can be described by copolymerization statistics. From concentration‐dependent measurements, derived copolymerization parameters and DFT calculations, a mechanism for self‐assembly is developed that suggests a kinetically driven polymerization process in combination with thermodynamically controlled crystallization.

Recent Advances in Additive Manufacturing and 3D Bioprinting for Organs-On-A-Chip and Microphysiological Systems.

The re-creation of physiological cellular microenvironments that truly resemble complex in vivo architectures is the key aspect in the development of advanced in vitro organotypic tissue constructs. Among others, organ-on-a-chip technology has been increasingly used in recent years to create improved models for organs and tissues in human health and disease, because of its ability to provide spatio-temporal control over soluble cues, biophysical signals and biomechanical forces necessary to maintain proper organotypic functions. While media supply and waste removal are controlled by microfluidic channel by a network the formation of tissue-like architectures in designated micro-structured hydrogel compartments is commonly achieved by cellular self-assembly and intrinsic biological reorganization mechanisms. The recent combination of organ-on-a-chip technology with three-dimensional (3D) bioprinting and additive manufacturing techniques allows for an unprecedented control over tissue structures with the ability to also generate anisotropic constructs as often seen in in vivo tissue architectures. This review highlights progress made in bioprinting applications for organ-on-a-chip technology, and discusses synergies and limitations between organ-on-a-chip technology and 3D bioprinting in the creation of next generation biomimetic in vitro tissue models.

Novel Temperature-Responsive Rosin-Derived Supramolecular Hydrogels Constructed by New Semicircular Aggregates.

A highly water-soluble rosin-based surfactant (C14-MPA-Na) was synthesized. Novel temperature-responsive supramolecular hydrogels were further prepared using C14-MPA-Na. The microstructure and the mechanical properties of the hydrogels were investigated. Unexpectedly, instead of the long one-dimensional structure, a new kind of twisted semicircular aggregate was formed in the hydrogels, which was rarely reported. Besides, the hydrogels possessed excellent shear-recovery properties. Upon heating to 40 °C, the hydrogels transformed into viscoelastic solutions, which were constructed by worm-like micelles. By adjusting the temperature, the hydrogels and the viscoelastic solutions could be freely transformed. Nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy were used to further explore the possible self-assembly mechanism of C14-MPA-Na. The curved alkane chain which partially overlapped with rosin's rigid skeleton became stretched when heated to 40 °C. The introduction of the rosin rigid skeleton endowed the supramolecular hydrogels with a novel microstructure and contributed to the development of strategies for the utilization of forest resources.

The crystallization of decanoic acid/dopamine supramolecular self-assemblies in the presence of coacervates

HypothesisSupramolecular self-assemblies involving non-covalent interactions play important roles in material science as well as living systems as they result in unique properties and/or functions. However, understanding of their self-assembly mechanism and crystallization has remained rudimentary. ExperimentHere, we focus on biomolecular fatty acid and dopamine, which commonly exist in biological systems and closely related to neurodegenerative diseases, and investigate their self-assembly pathway by optical and fluorescence microscopy, DLS, SAXS, TEM, 2D-NMR, etc. FindingsIt is found that they could form the crystalline plates in solution or via a metastable liquid − liquid phase separation (LLPS). The nucleation and growth of crystalline plates observed occurs in solution or the dilute phase of LLPS, and not within the concentrated coacervate phase. This is because in coacervate, dopamine intercalates into fatty acid through hydrophobic and electrostatic interaction, which hinders the rearrangement of molecules and nucleation process, whereas in solution or dilute phase, they have the mobility to arrange into ordered structures to maximize electrostatic, hydrogen bonding and π-π interactions, leading to nucleation and crystallization. Moreover, the transitions between the coacervates and crystalline phase can be realized by adjusting the temperature. Our results shed light on the multistep nucleation in the presence of LLPS, as well as molecular mechanisms involved, thus further extending the nucleation–growth mechanisms.

A Self-Assembled Matrix System for Cell-Bioengineering Applications in Different Dimensions, Scales, and Geometries.

Stem cell bioengineering and therapy require different model systems and materials in different stages of development. If a chemically defined biomatrix system can fulfill most tasks, it can minimize the discrepancy among various setups. By screening biomaterials synthesized through a coacervation-mediated self-assembling mechanism, a biomatrix system optimal for 2D human mesenchymal stromal cell (hMSC) culture and osteogenesis is identified. Its utility for hMSC bioengineering is further demonstrated in coating porous bioactive glass scaffolds and nanoparticle synthesis for esiRNA delivery to knock down the SOX-9 gene with high delivery efficiency. The self-assembled injectable system is further utilized for 3D cell culture, segregated co-culture of hMSC with human umbilical vein endothelial cells (HUVEC) as an angiogenesis model, and 3D bioprinting. Most interestingly, the coating of bioactive glass with the self-assembled biomatrix not only supports the proliferation and osteogenesis of hMSC in the 3D scaffold but also induces the amorphous bioactive glass (BG) scaffold surface to form new apatite crystals resembling bone-shaped plate structures. Thus, the self-assembled biomatrix system can be utilized in various dimensions, scales, and geometries for many different bioengineering applications.

Self-Assembled Metal Nanoclusters: Driving Forces and Structural Correlation with Optical Properties.

Studies on self-assembly of metal nanoclusters (MNCs) are an emerging field of research owing to their significant optical properties and potential applications in many areas. Fabricating the desired self-assembly structure for specific implementation has always been challenging in nanotechnology. The building blocks organize themselves into a hierarchical structure with a high order of directional control in the self-assembly process. An overview of the recent achievements in the self-assembly chemistry of MNCs is summarized in this review article. Here, we investigate the underlying mechanism for the self-assembly structures, and analysis reveals that van der Waals forces, electrostatic interaction, metallophilic interaction, and amphiphilicity are the crucial parameters. In addition, we discuss the principles of template-mediated interaction and the effect of external stimuli on assembly formation in detail. We also focus on the structural correlation of the assemblies with their photophysical properties. A deep perception of the self-assembly mechanism and the degree of interactions on the excited state dynamics is provided for the future synthesis of customizable MNCs with promising applications.

Self‐Assembly of Helical Polymers and Oligomers to Create Liquid Crystalline Alignment for Anisotropic NMR Parameters

The measurement of anisotropic residual dipolar couplings (RDCs) parameters for the structure elucidation of organic molecules relies on suitable alignment media. Employment of self-assembled liquid crystalline systems to create anisotropic alignment can be an effective way to realize aligned samples and acquire RDCs. This Mini-review highlights the recent advances on amino acid-based helical polymers and supramolecular oligomers forming rigid, rod-like structures that aggregate into ordered liquid crystalline phases, including amino acid-based helical polyisocyanides, polyacetylenes, polypeptides, and oligopeptides assembled alignment media. The methodology for the determination of anisotropic liquid crystals is briefly discussed, and a summary of recent research progress in the enantiodifferentiation of helical polymers aligned media is followed. In addition, the self-assembled mechanism of oligopeptides and their RDCs structural analysis are also described.

A Palette of Fluorescent Aβ42 Peptides Labelled at a Range of Surface-Exposed Sites.

Fluorescence-based single molecule techniques provide important tools towards understanding the molecular mechanism of complex neurodegenerative diseases. This requires efficient covalent attachment of fluorophores. Here we create a series of cysteine mutants (S8C, Y10C, S26C, V40C, and A42C) of A42, involved in Alzheimer’s disease, based on exposed positions in the fibril structure and label them with the Alexa-fluorophores using maleimide chemistry. Direct stochastic optical reconstruction microscopy imaging shows that all the labelled mutants form fibrils that can be detected by virtue of Alexa fluorescence. Aggregation assays and cryo-electron micrographs establish that the careful choice of labelling position minimizes the perturbation of the aggregation process and fibril structure. Peptides labelled at the N-terminal region, S8C and Y10C, form fibrils independently and with wild-type. Peptides labelled at the fibril core surface, S26C, V40C and A42C, form fibrils only in mixture with wild-type peptide. This can be understood on the basis of a recent fibril model, in which S26, V40 and A42 are surface exposed in two out of four monomers per fibril plane. We provide a palette of fluorescently labelled A42 peptides that can be used to gain understanding of the complex mechanisms of A42 self-assembly and help to develop a more targeted approach to cure the disease.

A Contrastive Study of Self-Assembly and Physical Blending Mechanism of TiO2 Blended Polyethersulfone Membranes for Enhanced Humic Acid Removal and Alleviation of Membrane Fouling.

In this study, membrane fabrication was achieved by two different methods: (i) self-assembly and (ii) physical blending of TiO2 in PES membrane for humic acid filtration. The TiO2 nanoparticles were self-assembled by using TBT as the precursor and pluronic F127 as triblock copolymers around the membrane pores. This was achieved by manipulating the hydrolysis and condensation reaction of TBT precursors during the non-solvent induced phase separation (NIPS) process. On the other hand, the TiO2 was physically blended as a comparison to the previous method. The characteristic of the membrane was analysed to explore the possibility of enhancing the membrane antifouling mechanism and the membrane flux. The membrane morphology, pore size, porosity, and contact angle were characterised. Both methods proved to be able to enhance the antifouling properties and flux performance. The HA rejection increased up to 95% with membrane flux 55.40 kg m−2 h−1. The rejection rate was not significantly improved for either method. However, the antifouling characteristic for the self-assembly TiO2/PES membrane was better than the physically blended membrane. This was found to be due to the high surface hydrophilicity of the MM membrane, which repelled the hydrophobic HA and consequently blocked the HA adsorption onto the surface.

Radial growth kinetics of epitaxial pyrolytic carbon layers deposited on carbon nanotube surfaces by non-catalytic pyrolysis

Chemical vapor deposition of pyrolytic carbon (PyC) onto carbon nanotube (CNT) surfaces by hydrocarbon pyrolysis can thicken the nanotube diameter until the desirable size. Vapor-induced thickening of CNTs may require no metal catalysts because the CNT-templated growth can easily convert PyC deposits into epitaxial graphene shells. However, little work has been done on the kinetics of the vapor-induced CNT thickening process during the non-catalytic pyrolysis. In this study, we discuss the growth mechanism of epitaxial PyC layers on CNT surfaces achieved by the low-pressure (≤1.5 kPa) pyrolysis of ethylene, which is distinct from previous studies using much higher gas pressures (4–100 kPa) for the PyC deposition. The average thickness of deposited PyC layers is calculated by analyzing the transmission electron microscopy images of PyC-coated CNTs. The crystallinity of PyC-coated CNTs is evaluated by Raman spectroscopy and X-ray diffraction. The thickness of PyC layers on CNT surfaces can be adjusted by simply changing the growth time under typical pyrolysis parameters (800 °C-1.5 kPa of ethylene). We find a two-stage nonlinear behavior to describe the growth kinetics of PyC layers, indicating that the radial growth rate of PyC layers can be influenced by the number of surface active sites. This study reveals the self-assembly mechanism of graphitic layers on the CNT template, which is expected to promote the diameter-controlled synthesis of CNTs.

Programmable Transient Supramolecular Chiral G-quadruplex Hydrogels by a Chemically Fueled Non-equilibrium Self-Assembly Strategy.

The temporal and spatial control of natural systems has aroused great interest for the creation of synthetic mimics. By using boronic ester based dynamic covalent chemistry and coupling it with an internal pH feedback system, we have developed a new chemically fueled reaction network for non-equilibrium supramolecular chiral G-quadruplex hydrogels with programmable lifetimes from minutes, to hours, to days, as well as high transparency and conductivity, excellent injectability, and rapid self-healing properties. The system can be controlled by the kinetically controlled in situ formation and dissociation of dynamic boronic ester bonds between the cis-diol of guanosine (G) and 5-fluorobenzoxaborole (B) in the presence of chemical fuels (KOH and 1,3-propanesultone), thereby leading to a precipitate-solution-gel-precipitate cycle under non-equilibrium conditions. A combined experimental-computational approach showed the underlying mechanism of the non-equilibrium self-assembly involves aggregation and disaggregation of right-handed helical G-quadruplex superstructures. The proposed dynamic boronic ester-based non-equilibrium self-assembly strategy offers a new option to design next-generation adaptive and interactive smart materials.

Cyclic peptides nanospheres: A ‘2-in-1′ self-assembled delivery system for targeting nucleus and cytoplasm

Vascular endothelial growth factor (VEGF) is considered as one of the vital growth factors for angiogenesis, which is primarily responsible for the progress and maintenance of new vascular network in tumor. Numerous studies report that inhibition of VEGF-induced angiogenesis is a potent technique for cancer suppression. Recently, RNA interference, especially small interfering RNA (siRNA) signified a promising approach to suppress the gene expression. However, the clinical implementation of biological macromolecules such as siRNA is significantly limited because of stability and bioavailability issues. Herein, self-assembled peptide nanospheres have been generated from L,L-cyclic peptides using hydrophobic (Trp), positively charged (Arg) and cysteine (Cys) amino acid residues and demonstrated as vehicles for intracellular delivery of VEGF siRNA and VEGF antisense oligonucleotide. Formation of peptide nanostructures is confirmed by HR-TEM, AFM, SEM and DLS analysis. Possible mechanism of self-assembly of the cyclic peptides and their binding with macromolecules are demonstrated by in-silico analysis. Gel electrophoresis reveals that the newly generated peptide based organic materials exhibit strong binding affinity toward siRNAs / antisense oligonucleotides (ASOs) at optimum concentration. Flow cytometry and confocal microscopy results confirm the efficiency of the new biomaterials toward the intracellular delivery of fluorescent labeled siRNA / ASOs. Furthermore, VEGF expression evaluated by western blot and RT-PCR upon the delivery of functional VEGF siRNA/ASOs suggests that very low concentrations of VEGF siRNA/ASOs cause significant gene knockdown at protein and mRNA levels, respectively.

The remarkable role of hydrogen bond, halogen, and solvent effect on self-healing supramolecular gel

Self-healing supramolecular gels of low-molecular-weight (LMW) molecules are smart soft materials; however, the development of self-healing LMW gelator is still a challenging task because of the lack of in-depth studies about self-healing mechanisms of LMW gels and the solvent effect on gel properties. Therefore, herein a different perspective was used to study a family of D-gluconic acetal-based gelators with variable structural fragments in 14 different solvents, and a more detailed understanding of self-assembly and self-healing mechanism of supramolecular gels was attained. Based on the critical gelation concentration, phase transition temperature, and rheological data, A8 bearing an amide group in side chain and two chlorine atoms linked to benzene ring was found to be an outstanding gelator, which could form gels with good self-healing ability in a variety of solvents. Interestingly, A8 gel formed in n-BuOH demonstrates high transparency, good mechanical strength, self-supporting behavior, and great self-healing ability from mechanical damage. Based on the Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and theoretical calculation analysis, the self-assembly and self-healing mechanisms of A8 gel were proposed, indicating that a combination of hydrogen bonding and halogen effect was responsible for the efficient self-healing behavior of supramolecular gel. Furthermore, the analysis of solvent parameters indicated that the dispersion force of solvent favored gelators to self-assemble, hydrogen bonding donor ability of solvent mainly affected the formation of one-dimensional assembly, and hydrogen bonding receptor ability and polarity of solvent mainly influenced the supramolecular interactions among assemblies, significantly intervening the self-healing ability of gels. Overall, this study provides a new perspective to the understanding of gelator structure–property correlation in solvents and sheds light for future development of self-healing supramolecular gels.

Microwave-assisted synthesis of self-assembly urchin-like ruthenium nanostructures in benzyl alcohol-glycerol mixed solvents

In this study, urchin-like ruthenium nanostructures (Ru NS), with an average size of approximately 30.2 nm, were successfully fabricated by reduction ruthenium chloride (RuCl3) in benzyl alcohol-glycerol mixed solvents, and using Polyvinylpyrrolidone (PVP) as the stabilizing agent under microwave irradiation for 240 s. The as-synthesized Ru NS were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), ultra violet-Visible (UV–Vis) absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectra. The results indicated that the as-prepared urchin-like Ru NS were self-assemblies organized by smaller primary nanoparticles with an average size of about 1.7 nm. Some key factors, such as the microwave assisted heating method, and the types of solvents, were identified affecting the successful synthesis of self-assembly urchin-like Ru NS. A possible growth mechanism for the novel Ru structures has been proposed, and the urchin-like Ru NS have been formed through a self-assembly aggregation mechanism driven by an overgrowth mode.

Tailoring Peptide Self-Assembly and Formation of 2D Nanoribbons on Mica and HOPG Surface.

Studying the interactions between biomolecules and material interfaces play a crucial role in the designing and synthesizing of functional bionanomaterials with tailored structure and function. Previously, a lot of studies were performed on the self-assembly of peptides in solution through internal and external stimulations, which mediated the creation of peptide nanostructures from zero-dimension to three-dimension. In this study, we demonstrate the self-assembly behavior of the GNNQQNY peptide on the surface of mica and highly oriented pyrolytic graphite through tailoring the self-assembly conditions. Various factors, such as the type of dissolvent, peptide concentration, pH value, and evaporation period on the formation of peptide nanofibers and nanoribbons with single- and bi-directional arrays are investigated. It is found that the creation of peptide nanoribbons on both mica and HOPG can be achieved effectively through adjusting and optimizing the experimental parameters. Based on the obtained results, the self-assembly and formation mechanisms of peptide nanoribbons on both material interfaces are discussed. It is expected that the findings obtained in this study will inspire the design of motif-specific peptides with high binding affinity towards materials and mediate the green synthesis of peptide-based bionanomaterials with unique function and application potential.

Ionic liquid-assisted synthesis of mesoporous polymers and carbon materials: the self-assembly mechanism.

Soft-templating synthesis has been widely employed to fabricate ordered mesoporous polymer and carbon materials with effectively tuneable pore sizes. However, the commonly used templating agents, block copolymers, are normally decomposed during the process, thus are barely recyclable; this increases the costs and hampers the scale-up feasibility. Therefore, it becomes imperative to seek promising alternatives; amphiphilic ionic liquids (ILs) are excellent candidates due to their good recyclability. This study explored the templating behaviour of IL templates for preparing mesoporous polymers and carbons. In details, the self-assembly of ternary systems (comprising of IL templates, precursors and solvent) were investigated by a combination of coarse-grained molecular dynamics (CGMD) simulations, density function theory (DFT) calculations and experimental techniques. The results indicate that the morphologies of IL templates are tuneable not only by the adjustment of water content in the mixture but also by the selection of suitable precursors. Material precursors containing increasing numbers of hydroxyl moieties also induce various precursor-template spatial correlations, resulting in different topological structures of nanomaterials. This work presents a fundamental investigation into the mechanisms of templating synthesis with amphiphilic ILs as recyclable templates and gives insight into the effective design of coveted carbon nanomaterials for targeted applications.

Morphological studies of self-assembled cyclotides extracted from Viola odorata as novel versatile platforms in biomedical applications.

Self-assembling peptides have attracted researchers' attention recently. They are classified as biomedical materials with unique properties formed in response to environmental conditions. Cyclotides are macrocyclic plant-derived peptides containing 28-37 amino acids that have the ability to self-assemble. Herein, we investigated the effect of pH, time, and temperature on the self-assembling properties of the cyclotides extracted from Viola odorata. For this purpose, the cyclotides were dispersed in aqueous trifluoroacetic acid at pH 2, 4, or 6 and incubated at 25 or 37 °C for 1, 2, 3, 5, 7 or 10 days, and the morphology of the self-assembled structures was identified by optical microscopy, polarized optical microscopy, scanning electron microscopy, transmission electron microscopy, and fluorescence microscopy. At pH 2 and 4, the self-assembly process of cyclotides comprises a number of steps, starting with the formation of spherical peptide nanostructures followed by hierarchically assembled nanotubes, and then shifting to nanofibers after 10 days. At pH 6, amorphous structures were produced even after 10 days. The temperature also could affect the self-assembly mechanism of the cyclotides. At 25 °C, the spherical peptide micelles formed firstly and then merged to form nanotubes, while at 37 °C the cyclotides showed crystallization followed by an increase in length with time. The fluorescence microscopy images showed that the nanotubes could efficiently entrap the hydrophobic molecules of coumarin. This comparative study on the self-assembly of the cyclotides extracted from Viola odorata is the first example exploring the capacity of these cyclotides to adopt precise nanostructures. The nanotubes and nanofibers obtained with these cyclotides might find interesting applications in drug delivery and tissue engineering.