Randomizing the growth of silica nanofibers for whiteness.

In colloids, the shape influences the function. In silica, straight nanorods have already been synthesized from water-in-oil emulsions. By contrast, curly silica nanofibers have been less reported because the underlying growth mechanism remains unexplored, hindering further morphology control for applications.

Structural Color from Cellulose Nanocrystals or Chitin Nanocrystals: Self-Assembly, Optics, and Applications.

Widespread concerns over the impact of human activity on the environment have resulted in a desire to replace artificial functional materials with naturally derived alternatives. As such, polysaccharides are drawing increasing attention due to offering a renewable, biodegradable, and biocompatible feedstock for functional nanomaterials. In particular, nanocrystals of cellulose and chitin have emerged as versatile and sustainable building blocks for diverse applications, ranging from mechanical reinforcement to structural coloration.

Brilliant whiteness in shrimp from ultra-thin layers of birefringent nanospheres.

A fundamental question regarding light scattering is how whiteness, generated from multiple scattering, can be obtained from thin layers of materials. This challenge arises from the phenomenon of optical crowding, whereby, for scatterers packed with filling fractions higher than ~30%, reflectance is drastically reduced due to near-field coupling between the scatterers. Here we show that the extreme birefringence of isoxanthopterin nanospheres overcomes optical crowding effects, enabling multiple scattering and brilliant whiteness from ultra-thin chromatophore cells in shrimp.

A tunable reflector enabling crustaceans to see but not be seen.

Many oceanic prey animals use transparent bodies to avoid detection. However, conspicuous eye pigments, required for vision, compromise the organisms' ability to remain unseen. We report the discovery of a reflector overlying the eye pigments in larval decapod crustaceans and show how it is tuned to render the organisms inconspicuous against the background.

Topological invariance in whiteness optimisation.

Maximizing the scattering of visible light within disordered nano-structured materials is essential for commercial applications such as brighteners, while also testing our fundamental understanding of light-matter interactions. The progress in the research field has been hindered by the lack of understanding how different structural features contribute to the scattering properties. Here we undertake a systematic investigation of light scattering in correlated disordered structures.

Tuning the Color of Photonic Glass Pigments by Thermal Annealing.

Thermal or solvent annealing is commonly employed to enhance phase separation and remove defects in block copolymer (BCP) films, leading to well-resolved nanostructures. Annealing is of particular importance for photonic BCP materials, where large, well-ordered lamellar domains are required to generate strong reflections at visible wavelengths. However, such strategies have not been considered for porous BCP systems, such as inverse photonic glasses, where the structure (and thus the optical response) is no longer defined solely by the chemical compatibility of the blocks, but by the size and arrangement of voids within the BCP matrix.

Deconvoluting the Optical Response of Biocompatible Photonic Pigments.

To unlock the widespread use of block copolymers as photonic pigments, there is an urgent need to consider their environmental impact (cf. microplastic pollution). Here we show how an inverse photonic glass architecture can enable the use of biocompatible bottlebrush block copolymers (BBCPs), which otherwise lack the refractive index contrast needed for a strong photonic response.

Deconvoluting the Optical Response of Biocompatible Photonic Pigments.

To unlock the widespread use of block copolymers as photonic pigments, there is an urgent need to consider their environmental impact (cf. microplastic pollution). Here we show how an inverse photonic glass architecture can enable the use of biocompatible bottlebrush block copolymers (BBCPs), which otherwise lack the refractive index contrast needed for a strong photonic response.

Chiral self-assembly of cellulose nanocrystals is driven by crystallite bundles.

The transfer of chirality across length-scales is an intriguing and universal natural phenomenon. However, connecting the properties of individual building blocks to the emergent features of their resulting large-scale structure remains a challenge. In this work, we investigate the origins of mesophase chirality in cellulose nanocrystal suspensions, whose self-assembly into chiral photonic films has attracted significant interest.

Direct Observation of Topological Defects in Striped Block Copolymer Discs and Polymersomes.

Topology and defects are of fundamental importance for ordered structures on all length scales. Despite extensive research on block copolymer self-assembly in solution, knowledge about topological defects and their effect on nanostructure formation has remained limited. Here, we report on the self-assembly of block copolymer discs and polymersomes with a cylinder line pattern on the surface that develops specific combinations of topological defects to satisfy the Euler characteristics for closed spheres as described by Gauss-Bonnet theorem.

Marcromolecular Architecture and Encapsulation of the Anticancer Drug Everolimus Control the Self-Assembly of Amphiphilic Polypeptide-Containing Hybrids.

Macromolecular architecture plays an important role in the self-assembly process of block copolymer amphiphiles. Herein, two series of stimuli-responsive amphiphilic 3-miktoarm star hybrid terpolypeptides and their corresponding linear analogues were synthesized exhibiting the same overall composition and molecular weight but different macromolecular architecture. The macromolecular architecture was found to be a key parameter in defining the morphology of the nanostructures formed in aqueous solutions as well as to alter the self-assembly behavior of the polymers independently of their composition.

Efficient Encapsulation of Fluorinated Drugs in the Confined Space of Water-Dispersible Fluorous Supraparticles.

Fluorophobic-driven assemblies of gold nanomaterials were stabilized into water-dispersible fluorous supraparticles by the film-forming protein hydrophobin II. The strategy makes use of fluorous nanomaterials of different dimensions to engineer size and inner functionalization of the resulting confined space. The inner fluorous compartments allow efficient encapsulation and transport of high loadings of partially fluorinated drug molecules in water.

Reversible Supracolloidal Self-Assembly of Cobalt Nanoparticles to Hollow Capsids and Their Superstructures.

The synthesis and spontaneous, reversible supracolloidal hydrogen bond-driven self-assembly of cobalt nanoparticles (CoNPs) into hollow shell-like capsids and their directed assembly to higher order superstructures is presented. CoNPs and capsids form in one step upon mixing dicobalt octacarbonyl (Co CO ) and p-aminobenzoic acid (pABA) in 1,2-dichlorobenzene using heating-up synthesis without additional catalysts or stabilizers. This leads to pABA capped CoNPs (core ca.

Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains.

Self-assembly of block copolymers into well-defined, ordered arrangements of chemically distinct domains is a reliable strategy for preparing tailored nanostructures. Microphase separation results from the system, minimizing repulsive interactions between dissimilar blocks and maximizing attractive interactions between similar blocks. Supramolecular methods have also achieved this separation by introducing small-molecule additives binding specifically to one block by noncovalent interactions.

Template-Free Supracolloidal Self-Assembly of Atomically Precise Gold Nanoclusters: From 2D Colloidal Crystals to Spherical Capsids.

We report supracolloidal self-assembly of atomically precise and strictly monodisperse gold nanoclusters involving p-mercaptobenzoic acid ligands (Au -pMBA ) under aqueous conditions into hexagonally packed monolayer-thick two-dimensional facetted colloidal crystals (thickness 2.7 nm) and their bending to closed shells leading to spherical capsids (d ca. 200 nm), as controlled by solvent conditions.

Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology.

Block copolymers self-assemble into a variety of nanostructures that are relevant for science and technology. While the assembly of diblock copolymers is largely understood, predicting the solution assembly of triblock terpolymers remains challenging due to complex interplay of block/block and block/solvent interactions. Here we provide guidelines for the self-assembly of linear ABC triblock terpolymers into a large variety of multicompartment nanostructures with C corona and A/B cores.

Chiral Plasmonics Using Twisting along Cellulose Nanocrystals as a Template for Gold Nanoparticles.

The right-handed twist along aqueous dispersed cellulose nanocrystals allows right-handed chiral plasmonics upon electrostatic binding of gold nanoparticles in dilute environment, through tuning the particle sizes and concentrations. Simulations using nanoparticle coordinates from cryo-electron tomography confirm the experimental results. The finding suggests generalization for other chiral and helical colloidal templates for nanoscale chiral plasmonics.

Self-Organization of Gold Nanoparticle Assemblies with 3D Spatial Order and Their External Stimuli Responsiveness.

Gold nanoparticles (AuNP) with pyridyl end-capped polystyrenes (PS-4VP) as "quasi-monodentate" ligands self-assemble into ordered PS-4VP/AuNP nanostructures with 3D hexagonal spatial order in the dried solid state. The key for the formation of these ordered structures is the modulation of the ratio AuNP versus ligands, which proves the importance of ligand design and quantity for the preparation of novel ordered polymer/metal nanoparticle conjugates. Although the assemblies of PS-4VP/AuNP in dispersion lack in high dimensional order, strong plasmonic interactions are observed due to close contact of AuNP.

Self-Assembly of a Functional Oligo(Aniline)-Based Amphiphile into Helical Conductive Nanowires.

A tetra(aniline)-based cationic amphiphile, TANI-NHC(O)C5H10N(CH3)3(+)Br(-) (TANI-PTAB) was synthesized, and its emeraldine base (EB) state was found to self-assemble into nanowires in aqueous solution. The observed self-assembly is described by an isodesmic model, as shown by temperature-dependent UV-vis investigations. Linear dichroism (LD) studies, combined with computational modeling using time-dependent density functional theory (TD-DFT), suggests that TANI-PTAB molecules are ordered in an antiparallel arrangement within nanowires, with the long axis of TANI-PTAB arranged perpendicular to the nanowire long axis.

Complexation-Driven Mutarotation in Poly(L-proline) Block Copolypeptides.

Novel poly(L-lysine)-block-poly(L-proline) (PLL-b-PLP)-based materials with all PLP helical conformers, i.e., PLP II and the rare PLP I are here reported.

Dendronized Hyperbranched Macromolecules: Soft Matter with a Novel Type of Segmental Distribution.

Dendronization of a hyperbranched polyester with different generation dendrons leads to pseudo-dendritic structures. The hyperbranched core is modified by the divergent coupling of protected monomer units to the functional groups. Compared to dendrimers, the synthetic effort is significantly less, but the properties are very close to those of high-generation dendrimers.

Supramolecular amplification of amyloid self-assembly by iodination.

Amyloid supramolecular assemblies have found widespread exploitation as ordered nanomaterials in a range of applications from materials science to biotechnology. New strategies are, however, required for understanding and promoting mature fibril formation from simple monomer motifs through easy and scalable processes. Noncovalent interactions are key to forming and holding the amyloid structure together.

Extended self-assembled long periodicity and Zig-Zag domains from helix-helix diblock copolymer Poly(γ-benzyl-l-glutamate)-block-poly(O-benzyl-l-hydroxyproline).

We describe the synthesis and self-assembly of particularly high periodicity of diblock copolymers composed of poly(benzyl-l-hydroxyproline) (PBLHyP) and poly(γ-benzyl-l-glutamate) (PBLG), that is, two polypeptide blocks with dissimilar helical structures. The robust helicity of the PBLHyP block is driven by steric constraints of the repeat units, while PBLG forms α-helices driven by hydrogen bonding, allowing defects and deformations. Herein, high-molecular-weight diblock copolypeptides of PBLG-b-PBLHyP with three different volume fractions of the PBLHyP-blocks are discussed.

Hidden structural features of multicompartment micelles revealed by cryogenic transmission electron tomography.

The demand for ever more complex nanostructures in materials and soft matter nanoscience also requires sophisticated characterization tools for reliable visualization and interpretation of internal morphological features. Here, we address both aspects and present synthetic concepts for the compartmentalization of nanoparticle peripheries as well as their in situ tomographic characterization. We first form negatively charged spherical multicompartment micelles from ampholytic triblock terpolymers in aqueous media, followed by interpolyelectrolyte complex (IPEC) formation of the anionic corona with bis-hydrophilic cationic/neutral diblock copolymers.