Hierarchical Molecular Assembly Research Articles

Self-Assembly of Hierarchical High-χ Fluorinated Block Copolymers with an Orthogonal Smectic-within-Lamellae 3 nm Sublattice and Vertical Surface Orientation.

Hierarchical structure-within-structure assemblies offer a route toward increasingly complex and multifunctional materials while pushing the limits of block copolymer self-assembly. We present a detailed study of the self-assembly of a series of fluorinated high-χ block copolymers (BCPs) prepared via postmodification of a single poly(styrene)-block-poly(glycidyl methacrylate) (S-b-G) parent polymer with the fluorinated alkylthiol pendent groups containing 1, 6, or 8 fluorinated carbons (termed trifluoro-ethanethiol (TFET), perfluoro-octylthiol (PFOT), and perfluoro-decylthiol (PFDT), respectively). Bulk X-ray scattering of thermally annealed samples demonstrates hierarchical molecular assembly with phase separation between the two blocks and within the fluorinated block. The degree of ordering within the fluorinated block is highly sensitive to synthetic variation; a lamellar sublattice was formed for S-b-GPFOT and S-b-GPFDT. Thermal analyses of S-b-GPFOT reveal that the fluorinated block exhibits liquid crystal-like ordering. The complex thin-film self-assembly behavior of an S-b-GPFOT polymer was investigated using real-space (atomic force microscopy and scanning electron microscopy) and reciprocal-space (resonant soft X-ray scattering (RSoXS), grazing incidence small- and wide-angle scattering) measurements. After thermal annealing in nitrogen or vacuum, films thicker than 1.5 times the primary lattice spacing exhibit a 90-degree grain boundary, exposing a thin layer of vertical lamellae at the free interface, while exhibiting horizontal lamellae on the preferential (polystyrene brush) substrate. RSoXS measurements reveal the near-perfect orthogonality between the primary and sublattice orientations, demonstrating hierarchical patterning at the nanoscale.

What can molecular assembly learn from catalysed assembly in living organisms?

Molecular assembly is the process of organizing individual molecules into larger structures and complex systems. The self-assembly approach is predominantly utilized in creating artificial molecular assemblies, and was believed to be the primary mode of molecular assembly in living organisms as well. However, it has been shown that the assembly of many biological complexes is "catalysed" by other molecules, rather than relying solely on self-assembly. In this review, we summarize these catalysed-assembly (catassembly) phenomena in living organisms and systematically analyse their mechanisms. We then expand on these phenomena and discuss related concepts, including catalysed-disassembly and catalysed-reassembly. Catassembly proves to be an efficient and highly selective strategy for synergistically controlling and manipulating various noncovalent interactions, especially in hierarchical molecular assemblies. Overreliance on self-assembly may, to some extent, hinder the advancement of artificial molecular assembly with powerful features. Furthermore, inspired by the biological catassembly phenomena, we propose guidelines for designing artificial catassembly systems and developing characterization and theoretical methods, and review pioneering works along this new direction. Overall, this approach may broaden and deepen our understanding of molecular assembly, enabling the construction and control of intelligent assembly systems with advanced functionality.

Homochiral hierarchical molecular assemblies through dynamic combination of conformational states of a single chiral building block at the liquid/solid interface.

We herein report the construction of homochiral, hierarchical self-assembled molecular networks (SAMNs) at the liquid/graphite interface using a single molecular building block, a chiral dehydrobenzo[12]annulene (cDBA) derivative with three chiral alkoxy and three hydroxy groups positioned in an alternating manner on the DBA core. The cDBA molecules form homochiral hierarchical SAMNs consisting of triangular clusters of several sizes, the size of which can be tuned by solvent polarity and solute concentration, reaching periodicities as large as 9.3 nm. We demonstrate the successful transmission of chirality information from the single molecular level to the hierarchical SAMN level, in a process that is mediated by dynamic self-sorting.

Hierarchical chirality expression of gemini surfactant aggregates via equilibrium between chiral nucleotide and nonchiral mono-anions.

The assembling behaviors of nonchiral dicationic amphiphilic molecules (gemini) in the presence of the mixture of chiral anionic nucleotides and nonchiral anions are investigated. We demonstrate that subtle balance of various physico-chemical parameters and the competition between chiral and nonchiral anions at the interface of gemini assemblies influences the expression of molecular chirality at the micrometer scale through the hierarchical molecular assembly.

From Silk Spinning to 3D Printing: Polymer Manufacturing using Directed Hierarchical Molecular Assembly.

Silk spinning offers an evolution-based manufacturing strategy for industrial polymer manufacturing, yet remains largely inaccessible as the manufacturing mechanisms in biological and synthetic systems, especially at the molecular level, are fundamentally different. The appealing characteristics of silk spinning include the sustainable sourcing of the protein material, the all-aqueous processing into fibers, and the unique material properties of silks in various formats. Substantial progress has been made to mimic silk spinning in artificial manufacturing processes, despite the gap between natural and artificial systems. This report emphasizes the universal spinning conditions utilized by both spiders and silkworms to generate silk fibers in nature, as a scientific and technical framework for directing molecular assembly into high-performance structures. The preparation of regenerated silk feedstocks and mimicking native spinning conditions in artificial manufacturing are discussed, as is progress and challenges in fiber spinning and 3D printing of silk-composites. Silk spinning is a biomimetic model for advanced and sustainable artificial polymer manufacturing, offering benefits in biomedical applications for tissue scaffolds and implantable devices.

3D Printing of Silk Protein Structures by Aqueous Solvent-Directed Molecular Assembly.

Hierarchical molecular assembly is a fundamental strategy for manufacturing protein structures in nature. However, to translate this natural strategy into advanced digital manufacturing like three-dimensional (3D) printing remains a technical challenge. This work presents a 3D printing technique with silk fibroin to address this challenge, by rationally designing an aqueous salt bath capable of directing the hierarchical assembly of the protein molecules. This technique, conducted under aqueous and ambient conditions, results in 3D proteinaceous architectures characterized by intrinsic biocompatibility/biodegradability and robust mechanical features. The versatility of this method is shown in a diversity of 3D shapes and a range of functional components integrated into the 3D prints. The manufacturing capability is exemplified by the single-step construction of perfusable microfluidic chips which eliminates the use of supporting or sacrificial materials. The 3D shaping capability of the protein material can benefit a multitude of biomedical devices, from drug delivery to surgical implants to tissue scaffolds. This work also provides insights into the recapitulation of solvent-directed hierarchical molecular assembly for artificial manufacturing.

1-nm-Wide Hydrated Dipole Arrays Regulate AuNW Assembly on Striped Monolayers in Nonpolar Solvent

Summary We show that striped phases of horizontally oriented phospholipids presenting 1-nm-wide orientable dipole arrays can order and straighten flexible 2-nm-diameter gold nanowires (AuNWs) with lengths (up to 1 μm) that greatly exceed the template pitch (∼7.5 nm). AuNW ordering can extend over areas > 100 μm2. Whereas wires bundle in solution, with contact between ligand shells, wires adsorbing to the template separate to much larger center-to-center distances (e.g., 12–30 nm) near multiples of the template pitch, consistent with repulsive interactions between wires emerging during interactions with dipole arrays in the template. AuNW assembly was carried out in cyclohexane, a nonpolar solvent. Interestingly, we found that wire ordering was contingent on the extent of phospholipid headgroup hydration and the presence of excess oleylamine, which assembled into hemicylindrical micelles around the hydrated headgroups. Together, these components generated a protected polar environment that enabled the phospholipid headgroups to function collectively to regulate AuNW assembly.

Visualizing the coordination-spheres of photoexcited transition metal complexes with ultrafast hard X-rays.

The concept of coordination sphere (CS) is central to the rational development of hierarchical molecular assemblies in modern chemistry. Manipulating the organization around transition metal ions with covalent and supramolecular interactions is a general strategy that underlies most synthetic protocols. Achieving similar control for photoexcited molecular complexes is necessary to advance the design of light-driven functionalities. This objective calls for monitoring the ultrafast dynamics of the primary (1-CS) and the secondary (2-CS) coordination spheres on the atomic scale, which remains to date an important experimental challenge for short-lived species. In this work, transient wide-angle scattering of hard X-rays (25 keV) is employed with state-of-the-art AIMD simulations in order to visualize the 1-CS (solute-only) and the 2-CS (solvation cage) of the photoinduced high-spin (HS) state for [Fe(bpy)3]2+ (bpy = 2,2'-bipyridine) in aqueous solution. Correlating this structural information in real-space reveals the interlacing of the two CS, which in turn explains why solvation affects the photoinduced electronic and structural dynamics in this class of complexes. More generally, these results obtained for a prominent prototypical system in ultrafast X-ray sciences demonstrate the unique perspectives offered by this technique to gain the crucial knowledge about the multiscale solvation dynamics that is currently missing for controlling the solute-solvent interactions in advanced functional nano and biomaterials employed for photoconversion.

1B02 棒状分子の階層的分子集合によるディスコチック液晶の形成機構(液晶化学・材料,口頭発表,2015年日本液晶学会討論会)

1B02 棒状分子の階層的分子集合によるディスコチック液晶の形成機構(液晶化学・材料,口頭発表,2015年日本液晶学会討論会)

Elucidating "screw dislocation"-driven film formation of sodium thiosulphate with complex hierarchical molecular assembly.

Sodium thiosulphate (Na2S2O3) films were synthesized on carbon steel substrates through solution deposition, and a film formation growth mechanism is delineated in detail herein. Dislocation-driven film formation took place at the lower concentration of Na2S2O3 (0.1 M) studied, where screw dislocation loops were identified. Interestingly, we observed the co-existence of screw dislocation spiral loops and hierarchically-ordered molecular assembly in the film, and showed the importance of hierarchical morphology in the origin of screw dislocation. The screw dislocation loops were, however, distorted at the higher studied concentration of Na2S2O3 (0.5 M), and no hierarchical structures were formed. The mechanisms of film formation are discussed in detail and provide new insights into our understanding regarding morphology of the hierarchical molecular assembly, screw dislocation loop formation, and the role of chemical elements for their development. The main crystalline and amorphous phases in the surface films were identified as pyrite/mackinawite and magnetite. As sodium thiosulphate is widely used for energy, corrosion inhibition, nanoparticle synthesis and catalysis applications, the knowledge generated in this study is applicable to the fields of corrosion, materials science, materials chemistry and metallurgy.

Studies of the structure and phase transitions of nano-confined pentanedithiol and its application in directing hierarchical molecular assemblies on Au(1 1 1)

Directing molecular devices into pre-designed integrated electronic circuits while enforcing selectivity and hierarchy is an inherent challenge for molecular electronics. Here we explore ways to direct the assembly of electrically-active molecular monolayers into specific locations as well as controlling their internal organization. We have accomplished this by two consecutive surface reactions: (1) forming pentanedithiol (C5DT) domains within an inert alkanethiol self-assembled monolayer (SAM) on Au; and (2) selectively binding porphyrin derivatives to the C5DT domains. The C5DT domains were fabricated by phase segregation during co-adsorption from a mixed C5DT/dodecanethiol (C12) solution and nanografting with Atomic Force Microscopy (AFM). AFM revealed that co-absorbed and nanografted C5DT domains were in a standing-up phase and scanning tunneling microscopy (STM) showed that their molecular organization within about 5 nm, 40 nm, 50 nm and 120 nm domains, was dependent upon the size of the domain, such that structure of the C5DT transitions from ( × ) R30°, to (2 × 2), and ultimately to a disordered phase with increasing domain size. This is due to the varying degrees of influence of the surrounding C12; providing sufficient van der Waals interactions as well as a geometric confinement to stabilize the standing-up phase of the C5DT. Understanding the molecular configuration of dithiol SAMs affords their use as a reactive template to subsequently bind active head groups. As a proof of principle, porphyrins with a pendant pentafluorophenyl ring were attached to the C5DT domains by a ‘click’ reaction between the fluorinated ring and the free thiol on the surface. From AFM and STM, these porphyrin derivatives reacted selectively with the C5DT domains with some porphyrins binding directly to the C5DT, subsequently allowing additional localized porphyrin deposition through pi-stacking.

Approaches to Corneal Tissue Engineering: Top-down or Bottom-up?

Tissue engineering creates biological tissues that aim to improve the function of diseased or damaged tissues such as the cornea (the main refractive component of the eye). Traditional tissue engineering strategies employ a “top-down” approach, in which cells are seeded on a polymeric scaffold that they then populate and create the appropriate extracellular matrix (ECM) often with the aid of perfusion, growth factors and/or mechanical stimulation. However, in highly organised tissues, such as the cornea, top-down approaches have difficulty recreating intricate but necessary microstructural features.With the desire to create more complex corneal tissues with features such as anisotropic hierarchical molecular assemblies, appropriate mechanical properties, cell binding motifs and corneal specific morphology, we are developing tissue engineering techniques that are moving away from the traditional top-down approach and instead focusing on building modular micro-tissues with repeated functional units which facilitate a bottom-up approach.Here we report on the success and shortcomings of both top-down and bottom-up approaches to creating engineered corneal tissues. Specifically, we will discuss recent work demonstrating the importance of engineering corneal ECM with appropriate levels of tissue compliance using a top-down approach. We will then highlight a bottom-up approach, which focuses on fabricating discreet bio-prosthetic ECM building blocks (corneal lamellae) with specific micro-architectural features derived solely from human corneal keratocytes under serum free conditions using enzyme responsive templates. These building blocks will then be used to generate a whole cornea whilst maintaining the intricate architecture and complexity of native corneal ECM.

Forced To Align: Flow-Induced Long-Range Alignment of Hierarchical Molecular Assemblies from 2D to 3D

Nanostructured molecular thin films adsorbed on solid surfaces form the basis of numerous applications. Long-range order within adsorbed molecules is very often a desirable property for such systems. In this contribution, we report a simple and efficient method to fabricate well-aligned thin films of organic molecules over a few millimeter squares. The strategy involves use of capillary force in a two-step flow method to induce large-area alignment of multilayers of molecules at the organic liquid-solid interface. Furthermore, we also demonstrate the influence of alignment on the electron transport through these well-aligned thin films using scanning tunneling spectroscopy.

階層化高分子組織体を用いた電子機能材料

The most efficient electric devices in nature will be the light harvesting system in biological membrane. Photosensitive proteins complex, such as photosystem I (PS I), photosystem II (PS II), and electron transport proteins complex such as cytochrome were hierarchically assembled in the bilayer membrane based on their redox potentials. Electrons, which were produced by photoinduced electron transfer in PS II are unidirectionally transferred to cytochrome b6f then PS I following the potential gradient in the membrane. We can produce similar hierarchical molecular assemblies using the Langmuir-Blodgett (LB) technique. The unidirectional electron current flow has been achieved in hierarchical assembled LB films to produce efficient light-energy conversion devices. In this paper, we prepare hierarchical assembled polymer films using the LB technique. It has been reported that poly (N-dodecylacrylamide) forms a stable polymer monolayer “polymer nanosheets” at the air-water interface. Several electrofunctional polymer nanosheets were assembled in a tailor-made manner to achieve the unidirectional electron transfer. We applied the unidirectional electron transfer to produce other unique electrofunctional devices such as molecular memory and mutli-color electrochromism. The results indicate that we can produce unique electric devices by not just mimicking functions in nature but extracting the essence of their functions and applying them.

Self‐Cleaning Functional Molecular Materials

Clean and polish: The spontaneous hierarchical molecular assembly of a naphthalenediimide derivative is used to form microarrays by a simple solution-processing technique. This method is further employed to fabricate a self-cleaning surface with very low slide angle (3°) and contact angle hysteresis (1°).

Nanorods Formed from a New Class of Peptidomimetics

Although peptide amphiphiles have been explored as nanomaterials for different applications, nanostructures formed by hierarchical molecular assembly of sequence-specific peptidomimetics are much less developed. Such protein-like nanomaterials could enhance the current application of peptide-based amphiphiles by enriching the diversity of nanostructures, increasing in vivo stability for biomedical applications, and facilitating the understanding of biomacromolecular self-assembly. Herein we present a biomimetic γ-AApeptide amphiphile which forms nanorods. Our results demonstrate the capability of γ-AApeptide amphiphiles as a potential scaffold for the preparation of biomimetic and bioinspired nanostructures. The programmability and biocompatibility of γ-AApeptides could lead to novel nanomaterials for a wide variety of applications.