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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. Much of this interest arises from the tendency of these colloidally stable nanoparticles to self-organize in water into a lyotropic cholesteric liquid crystal, which can be readily manipulated in terms of its periodicity, structure, and geometry. Importantly, this helicoidal ordering can be retained into the solid-state, offering an accessible route to complex nanostructured films, coatings, and particles. In this review, the process of forming iridescent, structurally colored films from suspensions of cellulose nanocrystals (CNCs) is summarized and the mechanisms underlying the chemical and physical phenomena at each stage in the process explored. Analogy is then drawn with chitin nanocrystals (ChNCs), allowing for key differences to be critically assessed and strategies toward structural coloration to be presented. Importantly, the progress toward translating this technology from academia to industry is summarized, with unresolved scientific and technical questions put forward as challenges to the community.
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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. A library of photonic pigments is produced from poly(norbornene-graft-polycaprolactone)-block-poly(norbornene-graft-polyethylene glycol), with the color tuned via either the BBCP molecular weight or the processing temperature upon microparticle fabrication. The structure-optic relationship between the 3D porous morphology of the microparticles and their complex optical response is revealed by both an analytical scattering model and 3D finite-difference time domain (FDTD) simulations. Combined, this allows for strategies to enhance the color purity to be proposed and realized with our biocompatible BBCP system.
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Fótons , Plásticos , Norbornanos , Polietilenoglicóis , PolímerosRESUMO
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. In addition, it was found that the assemblies prepared from the star-shaped polymers showed superior tolerance against enzymatic degradation due to the increased corona block density on the outer surface of the nanoparticles. Encapsulation of the hydrophobic anticancer drug Everolimus resulted in the formation of intriguing non-spherical and non-symmetric pH-responsive nanostructures, such as "stomatocytes" and "multi-compartmentalized suprapolymersomes", while the pH-triggered release of the drug was also investigated. Owing to the similarities of the developed "stomatocytes" with red blood cells, in combination with their pH-responsiveness and superior stability over enzymatic degradation, they are expected to present advanced drug delivery properties and have the ability to bypass several extra- and intracellular barriers to reach and effectively treat cancer cells.
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Antineoplásicos , Everolimo , Hidrogéis , Nanopartículas/química , Peptídeos , Antineoplásicos/química , Antineoplásicos/farmacocinética , Preparações de Ação Retardada/síntese química , Preparações de Ação Retardada/química , Preparações de Ação Retardada/farmacocinética , Everolimo/química , Everolimo/farmacocinética , Humanos , Hidrogéis/síntese química , Hidrogéis/química , Hidrogéis/farmacocinética , Concentração de Íons de Hidrogênio , Neoplasias/tratamento farmacológico , Peptídeos/síntese química , Peptídeos/química , Peptídeos/farmacocinéticaRESUMO
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 (Co2 CO8 ) 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. 5â nm) with a narrow size distribution. They spontaneously assemble into tunable spherical capsids (d≈50-200â nm) with a few-layered shells, as driven by inter-nanoparticle hydrogen bonds thus warranting supracolloidal self-assembly. The capsids can be reversibly disassembled and reassembled by controlling the hydrogen bonds upon heating or solvent exchanges. The superparamagnetic nature of CoNPs allows magnetic-field-directed self-assembly of capsids to capsid chains due to an interplay of induced dipoles and inter-capsid hydrogen bonds. Finally, self-assembly on air-water interface furnishes lightweight colloidal framework films.
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Fluorophobic-driven assemblies of gold nanomaterials were stabilized into water-dispersible fluorous supraparticles by the film-forming protein hydrophobinâ 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.
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Benzoxazinas/química , Celecoxib/química , Flúor/química , Leflunomida/química , Alcinos , Ciclopropanos , Ouro/química , Halogenação , Substâncias Macromoleculares/química , Nanopartículas Metálicas/química , Tamanho da Partícula , Água/químicaRESUMO
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. Applying temperature as an external stimulus allows the reversible distortion of plasmonic interactions within the AuNP nanocomposite structures, which can be observed directly by naked eye. The modulation of the macroscopic optical properties accompanied by this structural distortion of plasmonic interaction opens up very interesting sensoric applications.
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Ouro/química , Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Polímeros/química , Espectrofotometria Ultravioleta , TemperaturaRESUMO
We report supracolloidal self-assembly of atomically precise and strictly monodisperse gold nanoclusters involving p-mercaptobenzoic acid ligands (Au102 -pMBA44 ) under aqueous conditions into hexagonally packed monolayer-thick two-dimensional facetted colloidal crystals (thickness 2.7â nm) and their bending to closed shells leading to spherical capsids (d ca. 200â nm), as controlled by solvent conditions. The 2D colloidal assembly is driven in template-free manner by the spontaneous patchiness of the pMBA ligands around the Au102 -pMBA44 nanoclusters preferably towards equatorial plane, thus promoting inter-nanocluster hydrogen bonds and high packing to planar sheets. More generally, the findings encourage to explore atomically precise nanoclusters towards highly controlled colloidal self-assemblies.
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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. Addition of either S- or R- camphorsulfonic acid (CSA) to TANI-PTAB converted TANI to the emeraldine salt (ES), which retained the ability to form nanowires. Acid doping of TANI-PTAB had a profound effect on the nanowire morphology, as the CSA counterions' chirality translated into helical twisting of the nanowires, as observed by circular dichroism (CD). Finally, the electrical conductivity of CSA-doped helical nanowire thin films processed from aqueous solution was 2.7 mS cm(-1). The conductivity, control over self-assembled 1D structure and water-solubility demonstrate these materials' promise as processable and addressable functional materials for molecular electronics, redox-controlled materials and sensing.
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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. Electrostatic supramolecular complexation of the adjacent cationic PLL with anionic molecules bearing DNA analogue H-bonding functionalities, such as deoxyguanosine monophosphate (dGMP), preserves the extended PLP II helix, and the complexed molecule is locked and held in position by orthogonal shape-persistent hydrogen-bonded dGMP ribbons and their extended π-stacking. The branched anionic surfactant dodecylbenzenesulfonic acid (DBSA) on the other hand, introduces periodicity frustration and interlayer plasticization, leading to a reversed mutarotation to the more compact PLP I helix by complexation, without external stimuli, and is here reported for the first time. We foresee that our findings can be used as a platform for novel molecularly adaptive functional materials, and could possibly give insight in many proline-related transmembrane biological functions.
Assuntos
Materiais Biocompatíveis/química , Peptídeos/química , Benzenossulfonatos/química , Polilisina/química , Eletricidade Estática , TensoativosRESUMO
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. The number of functional groups, molar mass, and rheology behavior even in the early generation (G1-G4) pseudo-dendrimers strongly resembles the behavior of dendrimers in higher generations (G5-G8). Comparison of the segmental and internal structure with perfect dendrimers is performed using SANS, dynamic light scattering and viscosity analysis, microscopy and molecular dynamics simulation. The interpretation of the results reveals unique structural characteristics arising from lower segmental density of the core, which turns into a soft nano-sphere with a smooth surface even in the first generation.
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Cellulose nanocrystals (CNCs) are high aspect ratio colloidal rods with nanoscale dimensions, attracting considerable interest recently due to their high mechanical properties, chirality, sustainability, and availability. In order to exploit them for advanced functions in new materials, novel supracolloidal concepts are needed to manipulate their self-assemblies. We report on exploring multivalent interactions to CNC surface and show that dendronized polymers (DenPols) with maltose-based sugar groups on the periphery of lysine dendrons and poly(ethylene-alt-maleimide) polymer backbone interact with CNCs. The interactions can be manipulated by the dendron generation suggesting multivalent interactions. The complexation of the third generation DenPol (G3) with CNCs allows aqueous colloidal stability and shows wrapping around CNCs, as directly visualized by cryo high-resolution transmission electron microscopy and electron tomography. More generally, as the dimensions of G3 are in the colloidal range due to their ~6 nm lateral size and mesoscale length, the concept also suggests supracolloidal multivalent interactions between other colloidal objects mediated by sugar-functionalized dendrons giving rise to novel colloidal level assemblies.
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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. For shorter PBLHyP blocks, hexagonal packing of PBLHyP helices is observed, while by increasing the length of the PBLHyP block, keeping at a similar PBLG block length, the packing is distorted. Zig-zag lamellar structures were obtained due to the mismatch in the packing periodicities of the PBLG and PBLHyP helices. The frustration that takes place at the interface leads the PBLHyP to tilt to match the PBLG periodicity. The zig-zag morphology is reported for the first time for high-molecular-weight helix-helix (rod-rod) copolypeptides, and the self-assembled periodicity is uncommonly large.
Assuntos
Hidroxiprolina/síntese química , Ácido Poliglutâmico/análogos & derivados , Sequências Hélice-Alça-Hélice , Ácido Poliglutâmico/síntese química , Estrutura Terciária de ProteínaRESUMO
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. Herein, we describe the synthetic protocol for silica nanofibers with a tunable curliness based on the control of the water-in-oil emulsion droplets. Systematically decreasing the droplet size and increasing their contact angle, the Brownian motion of the droplets intensifies during the silica growth, thus increasing the random curliness of the nanofibers. This finding is supported by simplistic theoretical arguments and experimentally verified by varying the temperature to finely tune the curliness. Assembling these nanofibers toward porous disordered films enhances multiple scattering in the visible range, resulting in increased whiteness in contrast to films constructed by spherical and rod-like building units, which can be useful for, e.g., coatings and pigments.
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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. We demonstrate that the scattering efficiency of disordered systems is mainly determined by topologically invariant features, such as the filling fraction and correlation length, and residual variations are largely accounted by the surface-averaged mean curvature of the systems. Optimal scattering efficiency can thus be obtained from a broad range of disordered structures, especially when structural anisotropy is included as a parameter. These results suggest that any disordered system can be optimised for whiteness and give comparable performance, which has far-reaching consequences for the industrial use of low-index materials for optical scattering.
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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. In this study, a demonstration of how the concept of "thermal annealing" can be applied to bottlebrush block copolymer (BBCP) microparticles with a photonic glass architecture is presented, enabling their coloration to be tuned from blue to red. By comparing biocompatible BBCPs with similar composition, but different thermal behavior, it is shown that this process is driven by both a temperature-induced softening of the BBCP matrix (i.e., polymer mobility) and the absence of microphase separation (enabling diffusion-induced swelling of the pores). Last, this concept is applied toward the production of a thermochromic patterned hydrogel, exemplifying the potential of such responsive biocompatible photonic-glass pigments toward smart labeling or anticounterfeiting applications.
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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. Strikingly, numerical simulations reveal that birefringence, originating from the spherulitic arrangement of isoxanthopterin molecules, enables intense broadband scattering almost up to the maximal packing for random spheres. This reduces the thickness of material required to produce brilliant whiteness, resulting in a photonic system that is more efficient than other biogenic or biomimetic white materials which operate in the lower refractive index medium of air. These results highlight the importance of birefringence as a structural variable to enhance the performance of such materials and could contribute to the design of biologically inspired replacements for artificial scatterers like titanium dioxide.
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We show double smectic-like self-assemblies in the solid state involving alternating layers of different polypeptide α-helices. We employed rod-coil poly(γ-benzyl l-glutamate)-block-poly(l-lysine) (PBLG-b-PLL) as the polymeric scaffold, where the PLL amino residues were ionically complexed to di-n-butyl phosphate (diC4P), di(2-ethylhexyl) phosphate (diC2/6P), di(2-octyldodecyl) phosphate (diC8/12P), or di-n-dodecyl phosphate (diC12P), forming PBLG-b-PLL(diC4P), PBLG-b-PLL(diC2/6P), PBLG-b-PLL(diC8/12P), and PBLG-b-PLL(diC12P) complexes, respectively. The complexes contain PBLG α-helices of fixed diameter and PLL-surfactant complexes adopting either α-helices of tunable diameters or ß-sheets. For PBLG-b-PLL(diC4P), that is, using a surfactant with short n-butyl tails, both blocks were α-helical, of roughly equal diameter and thus with minor packing frustrations, leading to alternating PBLG and PLL(diC4P) smectic layers of approximately perpendicular alignment of both types of α-helices. Surfactants with longer and branched alkyl tails lead to an increased diameter of the PLL-surfactant α-helices. Smectic alternating PBLG and PLL(diC2/6P) layers involve larger packing frustration, which leads to poor overall order and suggests an arrangement of tilted PBLG α-helices. In PBLG-b-PLL(diC8/12P), the PLL(diC8/12P) α-helices are even larger and the overall structure is poor. Using a surfactant with two linear n-dodecyl tails leads to well-ordered ß-sheet domains of PLL(diC12P), consisting of alternating PLL and alkyl chain layers. This dominates the whole assembly, and at the block copolypeptide length scale, the PBLG α-helices do not show internal order and have poor organization. Packing frustration becomes an important aspect to design block copolypeptide assemblies, even if frustration could be relieved by conformational imperfections. The results suggest pathways to control hierarchical liquid-crystalline assemblies by competing interactions and by controlling molecular packing frustrations.
Assuntos
Peptídeos/química , Ácido Poliglutâmico/análogos & derivados , Polilisina/química , Polímeros/química , Cristais Líquidos/química , Ácido Poliglutâmico/química , Estrutura Secundária de Proteína , Tensoativos/química , Água/químicaRESUMO
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. By correlating the ensemble behaviour in suspensions and films with a quantitative morphological analysis of the individual nanoparticles, we reveal an inverse relationship between the cholesteric pitch and the abundance of laterally-bound composite particles. These 'bundles' thus act as colloidal chiral dopants, analogous to those used in molecular liquid crystals, providing the missing link in the hierarchical transfer of chirality from the molecular to the colloidal scale.
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Cristais Líquidos , Nanopartículas , Celulose/química , Cristais Líquidos/química , Nanopartículas/química , Óptica e Fotônica , SuspensõesRESUMO
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. A library of photonic pigments is produced from poly(norbornene-graft-polycaprolactone)-block-poly(norbornene-graft-polyethylene glycol), with the color tuned via either the BBCP molecular weight or the processing temperature upon microparticle fabrication. The structure-optic relationship between the 3D porous morphology of the microparticles and their complex optical response is revealed by both an analytical scattering model and 3D finite-difference time domain (FDTD) simulations. Combined, this allows for strategies to enhance the color purity to be proposed and realized with our biocompatible BBCP system.