Triterpenoid Building Blocks for Functional Nanoscale Assemblies: A Review

Peer reviewe

Precision nanoengineering for functional self-assemblies across length scales

As nanotechnology continues to push the boundaries across disciplines, there is an increasing need for engineering nanomaterials with atomic-level precision for self-assembly across length scales, i.e., from the nanoscale to the macroscale. Although molecular self-assembly allows atomic precision, extending it beyond certain length scales presents a challenge. Therefore, the attention has turned to size and shape-controlled metal nanoparticles as building blocks for multifunctional colloidal self-assemblies. However, traditionally, metal nanoparticles suffer from polydispersity, uncontrolled aggregation, and inhomogeneous ligand distribution, resulting in heterogeneous end products. In this feature article, I will discuss how virus capsids provide clues for designing subunit-based, precise, efficient, and error-free self-assembly of colloidal molecules. The atomically precise nanoscale proteinic subunits of capsids display rigidity (conformational and structural) and patchy distribution of interacting sites. Recent experimental evidence suggests that atomically precise noble metal nanoclusters display an anisotropic distribution of ligands and patchy ligand bundles. This enables symmetry breaking, consequently offering a facile route for two-dimensional colloidal crystals, bilayers, and elastic monolayer membranes. Furthermore, inter-nanocluster interactions mediated via the ligand functional groups are versatile, offering routes for discrete supracolloidal capsids, composite cages, toroids, and macroscopic hierarchically porous frameworks. Therefore, engineered nanoparticles with atomically precise structures have the potential to overcome the limitations of molecular self-assembly and large colloidal particles. Self-assembly allows the emergence of new optical properties, mechanical strength, photothermal stability, catalytic efficiency, quantum yield, and biological properties. The self-assembled structures allow reproducible optoelectronic properties, mechanical performance, and accurate sensing. More importantly, the intrinsic properties of individual nanoclusters are retained across length scales. The atomically precise nanoparticles offer enormous potential for next-generation functional materials, optoelectronics, precision sensors, and photonic devices.Peer reviewe

Aging-Induced Structural Transition of Nanoscale Oleanolic Acid Amphiphiles and Selectivity against Gram-Positive Bacteria

Triterpenoids are among the largest groups of functional plant secondary metabolites but with intrinsically low water solubility. Because of their rigid backbone, multiple chiral centers, and functional groups, they are suitable for synthesizing water-soluble and conformationally rigid triterpenoid amphiphiles with unique self-assembly behavior. In this context, we present the aqueous self-assembly, structural transition, and antimicrobial properties of nanoscale oleanolic acid–spermine conjugates (2–4). The conjugates contain either one or two spermine moieties connected through a 1,4-disubstituted 1,2,3-triazole linker. We use cryogenic transmission electron microscopy (cryo-TEM) imaging to show that conjugates 2 and 3 self-assemble in water initially into kinetically favored metastable micellar nanoparticles (d ≈ 6–10 nm). The nanoparticles further reorganize to form thermodynamically stable helical nanofibers. Notably, cryo-TEM imaging also suggests the formation of spherulite-like structures. Time-dependent infrared (IR) spectroscopy reveals the role of hydration and dehydration in the structural transition of initial micelle-like structures into thermodynamically stable nanofibers. Electronic and vibrational circular dichroism (ECD and VCD, respectively) spectroscopy in the solution state suggests the formation of chiral superstructures with a left-handed helical twist. The conjugates display antibacterial properties with high selectivity against Gram-positive bacterial strains. The results help us understand fibrillar network formation in supramolecular gels, and demonstrate that the position and number of spermine groups influence the self-assembly behavior of the conjugates in aqueous media and their biological properties.acceptedVersionPeer reviewe

Cylindrical Zwitterionic Particles via Interpolyelectrolyte Complexation on Molecular Polymer Brushes

The fabrication of macromolecular architectures with high aspect ratio and well‐defined internal and external morphologies remains a challenge. The combination of template chemistry and self‐assembly concepts to construct peculiar polymer architectures via a bottom‐up approach is an emerging approach. In this study, a cylindrical template—namely a core–shell molecular polymer brush—and linear diblock copolymers (DBCP) associate to produce high aspect ratio polymer particles via interpolyelectrolyte complexation. Induced, morphological changes are studied using cryogenic transmission electron and atomic force microscopy, while the complexation is further followed by isothermal titration calorimetry and ξ‐potential measurements. Depending on the nature of the complexing DBCP, distinct morphological differences can be achieved. While polymers with a non‐ionic block lead to internal compartmentalization, polymers featuring zwitterionic domains lead to a wrapping of the brush template

Cellulose optical fiber for sensing applications

Cellulose materials offer new biodegradable alternatives for fabricating optical fibers for sensing applications. Unlike glass and polymer optical fibers, these environmentally friendly materials have intrinsic properties making them attractive candidates for functional optical fibers. Cellulose fibers are hygroscopic and thus can rapidly take water vapors from the surroundings and dry quickly. Cellulose-based optical fibers can be manufactured from regenerated cellulose or cellulose derivatives which offer a large property space. They can be resistant or soluble in water, and the refracting index of the material can be tuned as needed. In this work, feasibility for sensor applications of three different cellulose optical fibers have been tested: regenerated cellulose for water and humidity sensing, carboxymethyl cellulose for respiratory rate monitoring, and methylcellulose for short-range 150 Mbit/s signal transmission at 1310 nm. Therefore, fast signal transmission can be achieved with short cellulose-based sensor fibers. The work shows the scientific and technical potential of a novel optical material for photonics.acceptedVersionPeer reviewe

Self-Assembly of Precision Noble Metal Nanoclusters : Hierarchical Structural Complexity, Colloidal Superstructures, and Applications

Ligand protected noble metal nanoparticles are excellent building blocks for colloidal self-assembly. Metal nanoparticle self-assembly offers routes for a wide range of multifunctional nanomaterials with enhanced optoelectronic properties. The emergence of atomically precise monolayer thiol-protected noble metal nanoclusters has overcome numerous challenges such as uncontrolled aggregation, polydispersity, and directionalities faced in plasmonic nanoparticle self-assemblies. Because of their well-defined molecular compositions, enhanced stability, and diverse surface functionalities, nanoclusters offer an excellent platform for developing colloidal superstructures via the self-assembly driven by surface ligands and metal cores. More importantly, recent reports have also revealed the hierarchical structural complexity of several nanoclusters. In this review, the formulation and periodic self-assembly of different noble metal nanoclusters are focused upon. Further, self-assembly induced amplification of physicochemical properties, and their potential applications in molecular recognition, sensing, gas storage, device fabrication, bioimaging, therapeutics, and catalysis are discussed. The topics covered in this review are extensively associated with state-of-the-art achievements in the field of precision noble metal nanoclusters.acceptedVersionPeer reviewe

Crystalline cyclophane-protein cage frameworks

open10siCyclophanes are macrocyclic supramolecular hosts famous for their ability to bind atomic or molecular guests via noncovalent interactions within their well-defined cavities. In a similar way, porous crystalline networks, such as metal organic frameworks, can create microenvironments that enable controlled guest binding in the solid state. Both types of materials often consist of synthetic components, and they have been developed within separate research fields. Moreover, the use of biomolecules as their structural units has remained elusive. Here, we have synthesized a library of organic cyclophanes and studied their electrostatic self-assembly with biological metal-binding protein cages (ferritins) into ordered structures. We show that cationic pillar[S]arenes and ferritin cages form biohybrid cocrystals with an open protein network structure. Our cyclophane-protein cage frameworks bridge the gap between molecular frameworks and colloidal nanoparticle crystals and combine the versatility of synthetic supramolecular hosts with the highly selective recognition properties of biomolecules. Such host-guest materials are interesting for porous material applications, including water remediation and heterogeneous catalysis.openBeyeh N.K.; Nonappa; Liljestrom V.; Mikkila J.; Korpi A.; Bochicchio D.; Pavan G.M.; Ikkala O.; Ras R.H.A.; Kostiainen M.A.Beyeh, N. K.; Nonappa, ; Liljestrom, V.; Mikkila, J.; Korpi, A.; Bochicchio, D.; Pavan, G. M.; Ikkala, O.; Ras, R. H. A.; Kostiainen, M. A

DNA‐Origami‐Templated Growth of Multilamellar Lipid Assemblies

Lipids are important building blocks in cellular compartments, and therefore their self‐assembly into well‐defined hierarchical structures has gained increasing interest. Cationic lipids and unstructured DNA can co‐assemble into highly ordered structures (lipoplexes), but potential applications of lipoplexes are still limited. Using scaffolded DNA origami nanostructures could aid in resolving these drawbacks. Here, we have complexed DNA origami together with a cationic lipid 1,2‐dioleoly‐3‐trimethylammonium‐propane (DOTAP) and studied their self‐assembly driven by electrostatic and hydrophobic interactions. The results suggest that the DNA origami function as templates for the growth of multilamellar lipid structures and that the DNA origami are embedded in the formed lipid matrix. Furthermore, the lipid encapsulation was found to significantly shield the DNA origami against nuclease digestion. The presented complexation strategy is suitable for a wide range of DNA‐based templates and could therefore find uses in construction of cell‐membrane‐associated components.acceptedVersionPeer reviewe

Shell-Isolated Assembly of Atomically Precise Nanoclusters on Gold Nanorods for Integrated Plasmonic-Luminescent Nanocomposites

In this work, we integrate atomically precise noble metal nanoclusters (NCs) on gold nanorods (AuNRs) to create hybrid plasmonic-luminescent nanomaterials. Initially, we assemble luminescent Ag29(LA)12 NC (LA = lipoic acid) to silica shell-encapsulated AuNRs. The resulting nanostructure shows plasmon-enhanced luminescence in aqueous medium as well as in the solid state. Atomic precision of the fluorophores used in this case allows detailed characterization of individual nanocomposites by diverse techniques, including transmission electron microscopy (TEM) and 3D electron tomographic reconstruction. We extend this strategy to prepare similar structures with gold NC protected with bovine serum albumin (Au30BSA). These two examples demonstrate the generic nature of the present strategy in preparing plasmonic-luminescent hybrid nanostructures using atomically precise NCs.acceptedVersionPeer reviewe

Crown Ether-Capped Gold Nanoclusters as a Multimodal Platform for Bioimaging

The distinct polarity of biomolecule surfaces plays a pivotal role in their biochemistry and functions as it is involved in numerous processes, such as folding, aggregation, or denaturation. Therefore, there is a need to image both hydrophilic and hydrophobic bio-interfaces with markers of distinct responses to hydrophobic and hydrophilic environments. In this work, we present a synthesis, characterization, and application of ultrasmall gold nanoclusters capped with a 12-crown-4 ligand. The nanoclusters present an amphiphilic character and can be successfully transferred between aqueous and organic solvents and have their physicochemical integrity retained. They can serve as probes for multimodal bioimaging with light (as they emit near-infrared luminescence) and electron microscopy (due to the high electron density of gold). In this work, we used protein superstructures, namely, amyloid spherulites, as a hydrophobic surface model and individual amyloid fibrils with a mixed hydrophobicity profile. Our nanoclusters spontaneously stained densely packed amyloid spherulites as observed under fluorescence microscopy, which is limited for hydrophilic markers. Moreover, our clusters revealed structural features of individual amyloid fibrils at a nanoscale as observed under a transmission electron microscope. We show the potential of crown ether-capped gold nanoclusters in multimodal structural characterization of bio-interfaces where the amphiphilic character of the supramolecular ligand is required.publishedVersionPeer reviewe