Experimental and theoretical evidence for molecular forces driving surface segregation in photonic colloidal assemblies

Surface segregation in binary colloidal mixtures offers a simple way to control both surface and bulk properties without affecting their bulk composition. Here, we combine experiments and coarse-grained molecular dynamics (CG-MD) simulations to delineate the effects of particle chemistry and size on surface segregation in photonic colloidal assemblies from binary mixtures of melanin and silica particles of size ratio (Dlarge/Dsmall) ranging from 1.0 to similar to 2.2. We find that melanin and/or smaller particles segregate at the surface of micrometer-sized colloidal assemblies (supraballs) prepared by an emulsion process. Conversely, no such surface segregation occurs in films prepared by evaporative assembly. CG-MD simulations explain the experimental observations by showing that particles with the larger contact angle (melanin) are enriched at the supraball surface regardless of the relative strength of particle-interface interactions, a result with implications for the broad understanding and design of colloidal particle assemblies

Blending block copolymer micelles in solution ; obstacles of blending

Amphiphilic block copolymers can assemble into a variety of structures on the nanoscale in selective solvent. The micelle blending protocol offers a simple unique route to reproducibly produce polymer nanostructures. Here we expand this blending protocol to a range of polymer micelle systems and self-assembly routes. We found by exploring a range of variables that the systems must be able to reach global equilibrium at some point for the blending protocol to be successful. Our results demonstrate the kinetics requirements, specifically core block glass transition temperature, Tg, and length of the block limiting the exchange rates, for the blending protocol which can then be applied to a wide range of polymer systems to access this simple protocol for polymer self-assembly

Bioinspired bright noniridescent photonic melanin supraballs

Structural colors enable the creation of a spectrumof nonfading colors without pigments, potentially replacing toxic metal oxides and conjugated organic pigments. However, significant challenges remain to achieve the contrast needed for a complete gamut of colors and a scalable process for industrial application. We demonstrate a feasible solution for producing structural colors inspired by bird feathers. We have designed core-shell nanoparticles using high-refractive index (RI) (similar to 1.74) melanin cores and low-RI (similar to 1.45) silica shells. The design of these nanoparticles was guided by finite-difference time-domain simulations. These nanoparticles were self-assembled using a one-pot reverse emulsion process, which resulted in bright and noniridescent supraballs. With the combination of only two ingredients, synthetic melanin and silica, we can generate a full spectrum of colors. These supraballs could be directly added to paints, plastics, and coatings and also used as ultraviolet-resistant inks or cosmetics

High Relaxivity Gadolinium-Polydopamine Nanoparticles

AbstractThis study reports the preparation of a series of gadolinium‐polydopamine nanoparticles (GdPD‐NPs) with tunable metal loadings. GdPD‐NPs are analyzed by nuclear magnetic relaxation dispersion and with a 7‐tesla (T) magnetic resonance imaging (MRI) scanner. A relaxivity of 75 and 10.3 mM−1 s−1 at 1.4 and 7 T is observed, respectively. Furthermore, superconducting quantum interference device magnetometry is used to study intraparticle magnetic interactions and determine the GdPD‐NPs consist of isolated metal ions even at maximum metal loadings. From these data, it is concluded that the observed high relaxivities arise from a high hydration state of the Gd(III) at the particle surface, fast rate of water exchange, and negligible antiferromagnetic coupling between Gd(III) centers throughout the particles. This study highlights design parameters and a robust synthetic approach that aid in the development of this scaffold for T1‐weighted, high relaxivity MRI contrast agents

Structural Color Production in Melanin-based Disordered Colloidal Nanoparticle Assemblies in Spherical Confinement

Melanin is a ubiquitous natural pigment that exhibits broadband absorption and high refractive index. Despite its widespread use in structural color production, how the absorbing material, melanin, affects the generated color is unknown. Using a combined molecular dynamics and finite-difference time-domain computational approach, this paper investigates structural color generation in one-component melanin nanoparticle-based supra-assemblies (called supraballs) as well as binary mixtures of melanin and silica (non-absorbing) nanoparticle-based supraballs. Experimentally produced one-component melanin and one-component silica supraballs, with thoroughly characterized primary particle characteristics using neutron scattering, produce reflectance profiles similar to the computational analogues, confirming that the computational approach correctly simulates both absorption and multiple scattering from the self-assembled nanoparticles. These combined approaches demonstrate that melanin's broadband absorption increases the primary reflectance peak wavelength, increases saturation, and decreases lightness factor. In addition, the dispersity of nanoparticle size more strongly influences the optical properties of supraballs than packing fraction, as evidenced by production of a larger range of colors when size dispersity is varied versus packing fraction. For binary melanin and silica supraballs, the chemistry-based stratification allows for more diverse color generation and finer saturation tuning than does the degree of mixing/demixing between the two chemistries.Comment: 40 pages, Figure

Modeling Structural Colors from Disordered One-Component Colloidal Nanoparticle-based Supraballs using Combined Experimental and Simulation Techniques

Bright, saturated structural colors in birds have inspired synthesis of self-assembled, disordered arrays of assembled nanoparticles with varied particle spacings and refractive indices. However, predicting colors of assembled nanoparticles, and thereby guiding their synthesis, remains challenging due to the effects of multiple scattering and strong absorption. Here, we use a computational approach to first reconstruct the nanoparticles' assembled structures from small-angle scattering measurements and then input the reconstructed structures to a finite-difference time-domain method to predict their color and reflectance. This computational approach is successfully validated by comparing its predictions against experimentally measured reflectance and provides a pathway for reverse engineering colloidal assemblies with desired optical and photothermal properties.Comment: 14 pages, 3 figures, 1 ToC figur

Mechanism of Structural Colors in Binary Mixtures of Nanoparticle-based Supraballs

Inspired by structural colors in avian species, various synthetic strategies have been developed to produce non-iridescent, saturated colors using nanoparticle assemblies. Mixtures of nanoparticles varying in particle chemistry (or complex refractive indices) and particle size have additional emergent properties that impact the color produced. For such complex multi-component systems, an understanding of assembled structure along with a robust optical modeling tool can empower scientists to perform intensive structure-color relationship studies and fabricate designer materials with tailored color. Here, we demonstrate how we can reconstruct the assembled structure from small-angle scattering measurements using the computational reverse-engineering analysis for scattering experiments (CREASE) method and then use the reconstructed structure in finite-difference time-domain (FDTD) calculations to predict color. We successfully, quantitatively predict experimentally observed color in mixtures containing strongly absorbing melanin nanoparticles and demonstrate the influence of a single layer of segregated nanoparticles on color produced. The versatile computational approach presented in this work is useful for engineering synthetic materials with desired colors without laborious trial and error experiments.Comment: 23 Pages, 5 Figures, 1 ToC Figur

Structure and Function of Iron-Loaded Synthetic Melanin

We describe a synthetic method for increasing and controlling the iron loading of synthetic melanin nanoparticles and use the resulting materials to perform a systematic quantitative investigation on their structure 12property relationship. A comprehensive analysis by magnetometry, electron paramagnetic resonance, and nuclear magnetic relaxation dispersion reveals the complexities of their magnetic behavior and how these intraparticle magnetic interactions manifest in useful material properties such as their performance as MRI contrast agents. This analysis allows predictions of the optimal iron loading through a quantitative modeling of antiferromagnetic coupling that arises from proximal iron ions. This study provides a detailed understanding of this complex class of synthetic biomaterials and gives insight into interactions and structures prevalent in naturally occurring melanins

Optical monitoring of polymerizations in droplets with high temporal dynamic range

The ability to optically monitor a chemical reaction and generate an in situ readout is an important enabling technology, with applications ranging from the monitoring of reactions in flow, to the critical assessment step for combinatorial screening, to mechanistic studies on single reactant and catalyst molecules. Ideally, such a method would be applicable to many polymers and not require only a specific monomer for readout. It should also be applicable if the reactions are carried out in microdroplet chemical reactors, which offer a route to massive scalability in combinatorial searches. We describe a convenient optical method for monitoring polymerization reactions, fluorescence polarization anisotropy monitoring, and show that it can be applied in a robotically generated microdroplet. Further, we compare our method to an established optical reaction monitoring scheme, the use of Aggregation-Induced Emission (AIE) dyes, and find the two monitoring schemes offer sensitivity to different temporal regimes of the polymerization, meaning that the combination of the two provides an increased temporal dynamic range. Anisotropy is sensitive at early times, suggesting it will be useful for detecting new polymerization “hits” in searches for new reactivity, while the AIE dye responds at longer times, suggesting it will be useful for detecting reactions capable of reaching higher molecular weights

Feature-interaction detection based on feature-based specifications

A Gd3+-coordinated polymerizable analogue of the MRI contrast agent Gd-DOTA was used to prepare amphiphilic block copolymers, with hydrophilic blocks composed entirely of the polymerized contrast agent. The resulting amphiphilic block copolymers assemble into nanoparticles (NPs) of spherical- or fibril-shape, each demonstrating enhanced relaxivity over Gd-DOTA. As an initial examination of their behavior in vivo, intraperitoneal (IP) injection of NPs into live mice was performed, showing long IP residence times, observed by MRI. Extended residence times for particles of well-defined morphology may represent a valuable design paradigm for treatment or diagnosis of peritoneal malignances