193 research outputs found
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
Cylindrical Zwitterionic Particles via Interpolyelectrolyte Complexation on Molecular Polymer Brushes
The fabrication of macromolecular architectures with high aspect ratio and wellâdefined internal and external morphologies remains a challenge. The combination of template chemistry and selfâassembly concepts to construct peculiar polymer architectures via a bottomâup approach is an emerging approach. In this study, a cylindrical templateânamely a coreâshell molecular polymer brushâand 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 Οâpotential measurements. Depending on the nature of the complexing DBCP, distinct morphological differences can be achieved. While polymers with a nonâionic block lead to internal compartmentalization, polymers featuring zwitterionic domains lead to a wrapping of the brush template
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
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 acidâspermine conjugates (2â4). 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 â 6â10 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
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
Inverse Thermoreversible Mechanical Stiffening and Birefringence in a Methylcellulose/Cellulose Nanocrystal Hydrogel
We show that composite hydrogels comprising methyl cellulose (MC) and cellulose nanocrystal (CNC) colloidal rods display a reversible and enhanced rheological storage modulus and optical birefringence upon heating, i.e., inverse thermoreversibility. Dynamic rheology, quantitative polarized optical microscopy, isothermal titration calorimetry (ITC), circular dichroism (CD), and scanning and transmission electron microscopy (SEM and TEM) were used for characterization. The concentration of CNCs in aqueous media was varied up to 3.5 wt % (i.e, keeping the concentration below the critical aq concentration) while maintaining the MC aq concentration at 1.0 wt %. At 20 degrees C, MC/CNC underwent gelation upon passing the CNC concentration of 1.5 wt %. At this point, the storage modulus (G') reached a plateau, and the birefringence underwent a stepwise increase, thus suggesting a percolative phenomenon. The storage modulus (G') of the composite gels was an order of magnitude higher at 60 degrees C compared to that at 20 degrees C. ITC results suggested that, at 60 degrees C, the CNC rods were entropically driven to interact with MC chains, which according to recent studies collapse at this temperature into ring-like, colloidal-scale persistent fibrils with hollow cross-sections. Consequently, the tendency of the MC to form more persistent aggregates promotes the interactions between the CNC chiral aggregates towards enhanced storage modulus and birefringence. At room temperature, ITC shows enthalpic binding between CNCs and MC with the latter comprising aqueous, molecularly dispersed polymer chains that lead to looser and less birefringent material. TEM, SEM, and CD indicate CNC chiral fragments within a MC/CNC composite gel. Thus, MC/CNC hybrid networks offer materials with tunable rheological properties and access to liquid crystalline properties at low CNC concentrations.Peer reviewe
DNAâOrigamiâTemplated Growth of Multilamellar Lipid Assemblies
Lipids are important building blocks in cellular compartments, and therefore their selfâassembly into wellâdefined hierarchical structures has gained increasing interest. Cationic lipids and unstructured DNA can coâassemble 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 1,2âdioleolyâ3âtrimethylammoniumâpropane (DOTAP) and studied their selfâassembly 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 DNAâbased templates and could therefore find uses in construction of cellâmembraneâassociated components.acceptedVersionPeer reviewe
Cationic polymers for DNA origami coating - examining their binding efficiency and tuning the enzymatic reaction rates
DNA origamis are fully tailored, programmable, biocompatible and readily functionalizable nanostructures that provide an excellent foundation for the development of sophisticated drug-delivery systems. However, the DNA origami objects suffer from certain drawbacks such as low cell-transfection rates and low stability. A great deal of studies on polymer-based transfection agents, mainly focusing on polyplex formation and toxicity, exists. In this study, the electrostatic binding between a brick-like DNA origami and cationic block-copolymers was explored. The effect of the polymer structure on the binding was investigated and the toxicity of the polymer-origami complexes evaluated. The study shows that all of the analyzed polymers had a suitable binding efficiency irrespective of the block structure. It was also observed that the toxicity of polymer-origami complexes was insignificant at the biologically relevant concentration levels. Besides brick-like DNA origamis, tubular origami carriers equipped with enzymes were also coated with the polymers. By adjusting the amount of cationic polymers that cover the DNA structures, we showed that it is possible to control the enzyme kinetics of the complexes. This work gives a starting point for further development of biocompatible and effective polycation-based block copolymers that can be used in coating different DNA origami nanostructures for various bioapplications.Peer reviewe
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