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The effect of the atmospheric condition on the extensive air shower analysis at the Telescope Array experiment
The accuracies in determination of air shower parameters such as longitudinal profiles or primary energies with the fluorescence detection technique are strongly dependent on atmospheric conditions of the molecular and aerosol components. Moreover, air fluorescence photon yield depends on the atmospheric density, and the transparency of the air for fluorescence photons depends on the atmospheric conditions from EAS to FDs. In this paper, we describe the atmospheric monitoring system in the Telescope Array (TA experiment), and the impact of the atmospheric conditions in air shower reconstructions. The systematic uncertainties of the determination of the primary cosmic ray energies and of the measurement of depth of maximum development (X{sub max}) of EASs due to atmospheric variance are evaluated by Monte Carlo simulation.
Assembly of multi-flavored two-dimensional colloidal crystals
We systematically investigate the assembly of binary multi-flavored colloidal mixtures in two dimensions. In these mixtures all pairwise interactions between species may be tuned independently. This introduces an additional degree of freedom over more traditional binary mixtures with fixed mixing rules, which is anticipated to open new avenues for directed self-assembly. At present, colloidal self-assembly into non-trivial lattices tends to require either high pressures for isotropically interacting particles, or the introduction of directionally anisotropic interactions. Here we demonstrate tunable assembly into a plethora of structures which requires neither of these conditions. We develop a minimal model that defines a three-dimensional phase space containing one dimension for each pairwise interaction, then employ various computational techniques to map out regions of this phase space in which the system self-assembles into these different morphologies. We then present a mean-field model that is capable of reproducing these results for size-symmetric mixtures, which reveals how to target different structures by tuning pairwise interactions, solution stoichiometry, or both. Concerning particle size asymmetry, we find that domains in this model's phase space, corresponding to different morphologies, tend to undergo a continuous “rotation” whose magnitude is proportional to the size asymmetry. Such continuity enables one to estimate the relative stability of different lattices for arbitrary size asymmetries. Owing to its simplicity and accuracy, we expect this model to serve as a valuable design tool for engineering binary colloidal crystals from multi-flavored components.
Topological Switching and Orbiting Dynamics of Colloidal Spheres Dressed with Chiral Nematic Solitons
Metastable configurations formed by defects, inclusions, elastic deformations and topological solitons in liquid crystals are a promising choice for building photonic crystals and metamaterials with a potential for new optical applications. Local optical modification of the director or introduction of colloidal inclusions into a moderately chiral nematic liquid crystal confined to a homeotropic cell creates localized multistable chiral solitons. Here we induce solitons that ‘‘dress’’ the dispersed spherical particles treated for tangential degenerate boundary conditions, and perform controlled switching of their state using focused optical beams. Two optically switchable distinct metastable states, toron and hopfion, bound to colloidal spheres into structures with different topological charges are investigated. Their structures are examined using Q-tensor based numerical simulations and compared to the profiles reconstructed from the experiments. A topological explanation of observed multistability is constructed.
Identification of a Frank–Kasper Z phase from shape amphiphile self-assembly
Frank-Kasper phases, a family of ordered structures formed from particles with spherical motifs, are found in a host of materials, such as metal alloys, inorganic colloids and various types of soft matter. All the experimentally observed Frank-Kasper phases can be constructed from the basic units of three fundamental structures called the A15, C15 and Z phases. The Z phase, typically observed in metal alloys, is associated with a relatively large volume ratio between its constituents, and this constraint inhibits its formation in most self-assembled single-component soft-matter systems. We have assembled a series of nanosized shape amphiphiles that comprise a triphenylene core and six polyhedral oligomeric silsesquioxane cages grafted onto it through linkers to give a variety of unconventional structures, which include the Z phase. Finally, this structure was obtained through fine tuning of the linker lengths between the core and the peripheral polyhedral oligomeric silsesquioxane cages, and exhibits a relatively large volume asymmetry between its constituent polyhedral particle motifs.
Structure and Dynamics of Bimodal Colloidal Dispersions in a Low-Molecular-Weight Polymer Solution
We present an experimental study of the structural and dynamical properties of bimodal, micrometersized colloidal dispersions (size ratio ≈ 2) in an aqueous solution of low-molecular weight polymer (polyethylene glycol 2000) using synchrotron ultra-small angle X-ray scattering (USAXS) and USAXSbased X-ray photon correlation spectroscopy. We fixed the volume fraction of the large particles at 5 % and systematically increased the volume fraction of the small particles from 0 % to 5 % to evaluate its effect on the structure and dynamics. The bimodal dispersions were homogenous through the investigated parameter space. We found that the partial structure factors can be satisfactorily retrieved for the bimodal colloidal dispersions using a Percus-Yevick hard sphere potential when the particle size distributions of the particles were taken into account. We also found that the partial structure factor between the large particles does not exhibit significant variation with increasing volume fraction of small particles, whereas the isothermal compressibility of the binary mixture was found to decrease with increasing volume fraction of small particles. The dynamics of single-component large particle dispersion obey the principles of de Gennes narrowing, where the wave vector dependence of the interparticle diffusion coefficient is inversely proportional to the interparticle structure factor. The dynamics of the bimodal dispersions demonstrate strong dependence on the fraction of small particles. As a result, we also made a comparison between the experimental effective dynamic viscosity of the bimodal dispersion with theoretical predictions, which suggest that the complex mutual interactions between large and small particles have a strong effect on the dynamic behaviors of bimodal dispersions.
Radiation-driven rotational motion of nanoparticles
Focused synchrotron beams can influence a studied sample via heating, or radiation pressure effects due to intensity gradients. The high angular sensitivity of rotational X-ray tracking of crystalline particles via their Bragg reflections can detect extremely small forces such as those caused by field gradients. By tracking the rotational motion of single-crystal nanoparticles embedded in a viscous or viscoelastic medium, the effects of heating in a uniform gradient beam and radiation pressure in a Gaussian profile beam were observed. Changes in viscosity due to X-ray heating were measured for 42 µm crystals in glycerol, and angular velocities of 10 −6 rad s −1 due to torques of 10 −24 N m were measured for 340 nm crystals in a colloidal gel matrix. These results show the ability to quantify small forces using rotation motion of tracer particles.
Structural Evolution of Layered Hybrid Lead Iodide Perovskites in Colloidal Dispersions
Controlling the structure of layered hybrid metal halide perovskites, such as the Ruddlesden-Popper (R-P) phases, is challenging because of their tendency to form mixtures of varying composition. Colloidal growth techniques, such as antisolvent precipitation, forms colloidal dispersions with properties that match bulk layered R-P phases, but controlling the composition of these particles remains challenging. Here, we explore the microstructure of particles of R-P phases of methylammonium lead iodide prepared by antisolvent precipitation from ternary mixtures of alkylammonium cations, where one cation can form perovskite phases (CH 3 NH 3 + ) and the other two promote layered structures as spacers (e.g. C 4 H 9 NH 3 + and C 12 H 25 NH 3 + ). We determine that alkylammonium spacers pack with constant methylene density in the R-P interlayer, and exclude interlayer solvent in dispersed colloids, regardless of length or branching. Using this result, we illustrate how the competition between cations that act as spacers between layers, or as grain- terminating ligands, determines the colloidal microstructure of layered R-P crystallites in solution. Optical measurements reveal that quantum well dimensions can be tuned by engineering the ternary cation composition. Transmission synchrotron wide-angle X-ray scattering and small angle neutron scattering reveal changes in the structure of colloids in solvent and after deposition into thin films. In particular, we find that spacers can alloy between R-P layers if they share common steric arrangements, but tend to segregate into polydisperse R-P phases if they do not mix. In conclusion, this study provides a framework to compare the microstructure of colloidal layered perovskites and suggests clear avenues to control phase and colloidal morphology.
Tunable emergent structures and traveling waves in mixtures of passive and contact-triggered-active particles
Systems with contact-triggered activity exhibit tunable structure and dynamics, that can be deployed to fabricate novel and reconfigurable colloidal materials.
Driving self-assembly and emergent dynamics in colloidal suspensions by time-dependent magnetic fields
In this review we discuss recent research on driving self assembly of magnetic particle suspensions subjected to alternating magnetic fields. The variety of structures and effects that can be induced in such systems is remarkably broad due to the large number of variables involved. The alternating field can be uniaxial, biaxial or triaxial, the particles can be spherical or anisometric, and the suspension can be dispersed throughout a volume or confined to a soft interface. In the simplest case the field drives the static or quasi-static assembly of unusual particle structures, such as sheets, networks and open-cell foams. More complex, emergent collective behaviors evolve in systems that can follow the time-dependent field vector. In these cases energy is continuously injected into the system and striking °ow patterns and structures can arise. In fluid volumes these include the formation of advection and vortex lattices. At air-liquid and liquid-liquid interfaces striking dynamic particle assemblies emerge due to the particle-mediated coupling of the applied field to surface excitations. These out-of-equilibrium interface assemblies exhibit a number of remarkable phenomena, including self-propulsion and surface mixing. In addition to discussing various methods of driven self assembly in magnetic suspensions, some of the remarkable properties of these novel materials are described.
Programmable self-assembly of diamond polymorphs from chromatic patchy particles
In this paper, we present a method of controlling polymorphism in self-assembly and apply it to the long-standing problem of assembly of a colloidal diamond. The latter is often viewed as the “holy grail” of the self-assembly field, due to the challenge that it presents as well as thanks to its potential as a step towards manufacturing of photonic band-gap materials. In our approach, we use a “chromatic” version of traditional building blocks, the so-called patchy particle. Namely, the individual patches that belong to the same particle in our model are distinguishable (“colored”) and their pairwise interactions are color dependent, which could be implemented with the help of DNA fictionalization. We propose a design procedure and verify it with the help of Brownian dynamics simulations. Not only are we able to “program” the self-assembly of a high-quality cubic diamond lattice, but a small modification of the coloring scheme also allows us to “reprogram” the system to assemble into the alternative polymorph, a hexagonal diamond.
Liquid Crystalline Order and Electric Switching of Upconversion Luminescence in Colloidal Nanorod Suspensions
The polarization-dependent photon upconversion luminescence properties of large-scale orientationally ordered soft matter systems formed by colloidal nanorods dispersed in an isotropic solvent are studied. The electrostatically charged photon-upconverting nanorods form an isotropic dispersion at low concentrations, whereas orientational order and a nematic phase emerge at high concentrations. When an alternating electric field is applied, particles align in the direction of the electric field in both nematic and isotropic phases, though the nature of this electric switching is different in these two phases. Owing to the long-range orientational order in the nematic phase, the upconversion luminescence from the particles is polarized without an external field. Polarization dependence of these properties can also be electrically induced in an isotropic phase of the colloidal nanorods. Further, the dynamics of switching of photon upconversion luminescence in both nematic and isotropic dispersions are explored and their potential technological uses are discussed.
Volume Labeling with Alexa-Fluor Dyes and Surface Functionalization of Highly Sensitive Fluorescent SiO2 Nanoparticles
A new synthesis approach is described that allows the direct incorporation of fluorescent labels into the volume or body of SiO2 nanoparticles. In this process, fluorescent Alexa Fluor dyes with different emission wavelengths were covalently incorporated into the SiO2 nanoparticles during their formation by the hydrolysis of tetraethoxysilane. The dye molecules were homogeneously distributed throughout the SiO2 nanoparticles. The quantum yields of the Alexa Fluor volume-labeled SiO2 nanoparticles were much higher than nanoparticles labeled using conventional organic dyes. The size of the resulting nanoparticles was controlled using microemulsion reaction media with sizes in the range of 20-100 nm and a polydispersity of <15%. In comparison with conventional surface tagged particles created by post-synthesis modification, this process maintains the physical and surface chemical properties that have the most pronounced effect on colloidal stability and interactions with their surroundings. These volume-labeled nanoparticles have proven to be extremely robust, showing excellent signal strength, negligible photobleaching, and minimal loss of functional organic components. The native or free surface of the volume-labeled particles can be altered to achieve a specific surface functionality without altering fluorescence. Their utility was demonstrated for visualizing the association of surface modified fluorescent particles with cultured macrophages. Differences in particle agglomeration and cell association were clearly associated with differences in observed nanoparticle toxicity. The capacity to maintain particle fluorescence while making significant changes to surface chemistry makes these particles extremely versatile and useful for studies of particle agglomeration, uptake, and transport in environmental and biological systems.
Process-Dependent Properties in Colloidally Synthesized “Giant” Core/Shell Nanocrystal Quantum Dots
Due to their characteristic bright and stable photoluminescence, semiconductor nanocrystal quantum dots (NQDs) have attracted much interest as efficient light emitters for applications from single-particle tracking to solid-state lighting. Despite their numerous enabling traits, however, NQD optical properties are frustratingly sensitive to their chemical environment, exhibit fluorescence intermittency ('blinking'), and are susceptible to Auger recombination, an efficient nonradiative decay process. Previously, we showed for the first time that colloidal CdSe/CdS core/shell nanocrystal quantum dots (NQDs) comprising ultrathick shells (number of shell monolayers, n, > 10) grown by protracted successive ionic layer adsorption and reaction (SILAR) leads to remarkable photostability and significantly suppressed blinking behavior as a function of increasing shell thickness. We have also shown that these so-called 'giant' NQDs (g-NQDs) afford nearly complete suppression of non-radiative Auger recombination, revealed in our studies as long biexciton lifetimes and efficient multiexciton emission. The unique behavior of this core/shell system prompted us to assess correlations between specific physicochemical properties - beyond shell thickness - and functionality. Here, we demonstrate the ability of particle shape/faceting, crystalline phase, and core size to determine ensemble and single-particle optical properties (quantum yield/brightness, blinking, radiative lifetimes). Significantly, we show how reaction process parameters (surface-stabilizing ligands, ligand:NQD ratio, choice of 'inert' solvent, and modifications to the SILAR method itself) can be tuned to modify these function-dictating NQD physical properties, ultimately leading to an optimized synthetic approach that results in the complete suppression of blinking. We find that the resulting 'guiding principles' can be applied to other NQD compositions, allowing us to achieve non-blinking behavior in the near-infrared. Lastly, in addition to realizing novel light-emission properties by refining nanoscale architectures at the single-NQD level, we also investigate collective properties by assembling our core/shell NQDs into larger scale arrays.
Theoretical and numerical investigations of inverse patchy colloids in the fluid phase
We investigate the structural and thermodynamic properties of a new class of patchy colloids, referred to as inverse patchy colloids (IPCs) in their fluid phase via both theoretical methods and simulations. IPCs are nano- or micro- meter sized particles with differently charged surface regions. We extend conventional integral equation schemes to this particular class of systems: our approach is based on the so-called multi-density Ornstein-Zernike equation, supplemented with the associative Percus-Yevick approximation (APY). To validate the accuracy of our framework, we compare the obtained results with data extracted from NpT and NVT Monte Carlo simulations. In addition, other theoretical approaches are used to calculate the properties of the system: the reference hypernetted-chain (RHNC) method and the Barker-Henderson thermodynamic perturbation theory. Both APY and RHNC frameworks provide accurate predictions for the pair distribution functions: APY results are in slightly better agreement with MC data, in particular at lower temperatures where the RHNC solution does not converge.
Control of Shell Morphology in p-n Heterostructured Water-Processable Semiconductor Colloids: Toward Extremely Efficient Charge Separation
This article describes p-n heterostructured water-borne semiconductor naonoparticles (NPs) with unique surface structures via control of shell morphology. The shell particles, comprising PC60-PC61BM composite, having n-type semiconductor characteristic, notably influence the charge carrier behavior in the core-shell NPs. A one- or two-phase methodology based on a PC60 surfactant-water phase and PC61BM n-type semiconductor-organic phase provided highly specific control over the shell structure of the NPs, which promoted their superior charge separation ability when combined with poly-3-hexyl-thiophene (P3HT). Moreover, the resulting water-borne NPs exhibit shell morphology-dependent carrier quenching and stability, which was characterized via luminescence studies paired with structural analysis. Corresponding to the results, outstanding performances of photovoltaic cells with over 5 % efficiency were achieved. The results suggest that the surrounding shell environments, such as the shell structure, and its electronic charge density, were crucial in determining the overall activity of the core-shell p-n heterostructured NPs. Thus, this work provides a new protocol in the current fields of water-based organic semiconductor colloids.
Salt-Induced Universal Slowing Down of the Short-Time Self-Diffusion of a Globular Protein in Aqueous Solution
The short-time self-diffusion D of the globular model protein bovine serum albumin in aqueous (D 2 O) solutions has been measured comprehensively as a function of the protein and trivalent salt (YCl 3 ) concentration, noted c p and c s , respectively. We observe that D follows a universal master curve D(c s ,c p ) = D(c s = 0,c p ) g(c s /c p ), where D(c s = 0,c p ) is the diffusion coefficient in the absence of salt and g(c s /c p ) is a scalar function solely depending on the ratio of the salt and protein concentration. This observation is consistent with a universal scaling of the bonding probability in a picture of cluster formation of patchy particles. In conclusion, the finding corroborates the predictive power of the description of proteins as colloids with distinct attractive ion-activated surface patches.
Nanoscale cooperative adsorption for materials control
Abstract Adsorption plays vital roles in many processes including catalysis, sensing, and nanomaterials design. However, quantifying molecular adsorption, especially at the nanoscale, is challenging, hindering the exploration of its utilization on nanomaterials that possess heterogeneity across different length scales. Here we map the adsorption of nonfluorescent small molecule/ion and polymer ligands on gold nanoparticles of various morphologies in situ under ambient solution conditions, in which these ligands are critical for the particles’ physiochemical properties. We differentiate at nanometer resolution their adsorption affinities among different sites on the same nanoparticle and uncover positive/negative adsorption cooperativity, both essential for understanding adsorbate-surface interactions. Considering the surface density of adsorbed ligands, we further discover crossover behaviors of ligand adsorption between different particle facets, leading to a strategy and its implementation in facet-controlled synthesis of colloidal metal nanoparticles by merely tuning the concentration of a single ligand.