Revisiting polymer surface adsorption with a level of quantification not possible at the time of earlier seminal contributions to this field, we employ fluorescence microscopy to quantify the in-plane diffusion of end-labeled polystyrene adsorbed onto quartz and mica from cyclohexane solution, mostly at 25 °C. Care is taken to prohibit a surface-hopping mechanism, and the experimental techniques are adapted to measurements that persist for up to a few days. The main conclusion is that we fail to observe a single Fickian diffusion coefficient: instead, diffusion displays a broad multicomponent spectrum, indicating that the heterogeneity of surface diffusion fails to average out even over these long times and over distances (∼600 nm, the diameter of a diffraction-limited spot) greatly exceeding the size of the polymer molecules. This holds generally when we vary the molecular weight, the surface roughness, and the temperature. It quantifies the long-believed scenario that strongly adsorbed polymer layers (monomer–surface interaction of more than 1kBT) intrinsically present diverse surface conformations that present heterogeneous environments to one another as they diffuse. Bearing in mind that in spite of adsorption from dilute solution the interfacial polymer concentration is high, ramifications of these findings are relevant to the interfacial mobility of polymer glasses, melts, and nanocomposites.

Entanglement in polymer and biological physics involves a state in which linear interthreaded macromolecules in isotropic liquids diffuse in a spatially anisotropic manner beyond a characteristic mesoscopic time and length scale (tube diameter). The physical reason is that linear macromolecules become transiently localized in directions transverse to their backbone but diffuse with relative ease parallel to it. Within the resulting broad spectrum of relaxation times there is an extended period before the longest relaxation time when filaments occupy a time-averaged cylindrical space of near-constant density. Here we show its implication with experiments based on fluorescence tracking of dilutely labeled macromolecules. The entangled pairs of aqueous F-actin biofilaments diffuse with separation-dependent dynamic cross-correlations that exceed those expected from continuum hydrodynamics up to strikingly large spatial distances of ≈15 µm, which is more than 104 times the size of the solvent water molecules in which they are dissolved, and is more than 50 times the dynamic tube diameter, but is almost equal to the filament length. Modeling this entangled system as a collection of rigid rods, we present a statistical mechanical theory that predicts these long-range dynamic correlations as an emergent consequence of an effective long-range interpolymer repulsion due to the de Gennes correlation hole, which is a combined consequence of chain connectivity and uncrossability. The key physical assumption needed to make theory and experiment agree is that solutions of entangled biofilaments localized in tubes that are effectively dynamically incompressible over the relevant intermediate time and length scales.

Monodisperse magnetic colloids are found to self-assemble into unusual crystals in the presence of rotating magnetic fields. First, we confirm a predicted phase transition (S. Jäger and S. H. L. Klapp, Soft Matter, 2011, 7, 6606–6616), directly coupled to the dynamic transition of single particle motion, from a disordered state to a hexagonal crystal. Next, going beyond what had been predicted, we report how hydrodynamic coupling produces shear melting, dislocations, and periodically mobile domain boundaries. These uniform magnetic colloids, whose structures are modulated in situ using the protocols described here, demonstrate a strategy of stimulus-response in the colloid domain with potential applications.

Colloidal metal–organic frameworks (CMOFs), nanoporous colloidal-sized crystals that are uniform in both size and polyhedral shape, are crystals composed of metal ions and organic bridging ligands, which can be used as building blocks for self-assembly in organic and aqueous liquids. They stand in contrast to conventional metal–organic frameworks (MOFs), which scientists normally study in the form of bulk crystalline powders. However, powder MOFs generally have random crystal size and shape and therefore do not possess either a definite mutual arrangement with adjacent particles or uniformity. CMOFs do have this quality, which can be important in vital uptake and release kinetics.In this Account, we present the diverse methods of synthesis, pore chemistry control, surface modification, and assembly techniques of CMOFs. In addition, we survey recent achievements and future applications in this emerging field. There is potential for a paradigm shift, away from using just bulk crystalline powders, towards using particles whose size and shape are regulated. The concept of colloidal MOFs takes into account that nanoporous MOFs, conventionally prepared in the form of bulk crystalline powders with random crystal size, shape, and orientation, may also form colloidal-sized objects with uniform size and morphology. Furthermore, the traditional MOF functions that depend on porosity present additional control over those MOF functions that depend on pore interactions. They also can enable controlled spatial arrangements between neighboring particles.To begin, we discuss progress regarding synthesis of MOF nano- and microcrystals whose crystal size and shape are well regulated. Next, we review the methods to modify the surfaces with dye molecules and polymers. Dyes are useful when seeking to observe nonluminescent CMOFs in situ by optical microscopy, while polymers are useful to tune their interparticle interactions. Third, we discuss criteria to assess the stability of CMOFs for various applications. In another section of this Account, we give examples of supracrystal assembly in liquid, on substrates, at interfaces, and under external electric fields. We end this Account with discussion of possible future developments, both conceptual and technological.

We investigate curvature-driven core–shell morphology that emerges when polycrystalline shells of ZIF-8 (zeolitic imidazolate framework coordination polymer) grow on colloid-sized particles. In early growth stages, the shell is continuous, but it transforms to yolk–shell, with neither sacrificial template nor core etching, because of geometrical frustration. A design rule is developed regarding how local surface curvature matters. Comparing shells grown on cubic, rod-like, and peanut-shaped hematite core particles, we validate the argument.

Particle tracking, the analysis of individual moving elements in time series of microscopic images, enables burgeoning new applications, but there is need to better resolve conformation and dynamics. Here we describe the advantages of Delaunay triangulation to extend the capabilities of particle tracking in three areas: (1) discriminating irregularly shaped objects, which allows one to track items other than point features; (2) combining time and space to better connect missing frames in trajectories; and (3) identifying shape backbone. To demonstrate the method, specific examples are given, involving analyzing the time-dependent molecular conformations of actin filaments and λ-DNA. The main limitation of this method, shared by all other clustering techniques, is the difficulty to separate objects when they are very close. This can be mitigated by inspecting locally to remove edges that are longer than their neighbors and also edges that link two objects, using methods described here, so that the combination of Delaunay triangulation with edge removal can be robustly applied to processing large data sets. As common software packages, both commercial and open source, can construct Delaunay triangulation on command, the methods described in this paper are both computationally efficient and easy to implement.

Revisiting polymer surface adsorption with a level of quantification not possible at the time of earlier seminal contributions to this field, we employ fluorescence microscopy to quantify the in-plane diffusion of end-labeled polystyrene adsorbed onto quartz and mica from cyclohexane solution, mostly at 25 °C. Care is taken to prohibit a surface-hopping mechanism, and the experimental techniques are adapted to measurements that persist for up to a few days. The main conclusion is that we fail to observe a single Fickian diffusion coefficient: instead, diffusion displays a broad multicomponent spectrum, indicating that the heterogeneity of surface diffusion fails to average out even over these long times and over distances (∼600 nm, the diameter of a diffraction-limited spot) greatly exceeding the size of the polymer molecules. This holds generally when we vary the molecular weight, the surface roughness, and the temperature. It quantifies the long-believed scenario that strongly adsorbed polymer layers (monomer–surface interaction of more than 1kBT) intrinsically present diverse surface conformations that present heterogeneous environments to one another as they diffuse. Bearing in mind that in spite of adsorption from dilute solution the interfacial polymer concentration is high, ramifications of these findings are relevant to the interfacial mobility of polymer glasses, melts, and nanocomposites.

Nanoscale dynamic heterogeneities in synthetic polymer solutions are detected using super-resolution optical microscopy. To this end, we map concentration fluctuations in polystyrene–toluene solutions with spatial resolution below the diffraction limit, focusing on critical fluctuations near the polymer overlap concentration, c*. Two-photon super-resolution microscopy was adapted to be applicable in an organic solvent, and a home-built STED-FCS system with stimulated emission depletion (STED) was used to perform fluorescence correlation spectroscopy (FCS). The polystyrene serving as the tracer probe (670 kg mol–1, radius of gyration RG ≈ 35 nm, end-labeled with a bodipy derivative chromophore) was dissolved in toluene at room temperature (good solvent) and mixed with matrix polystyrene (3,840 kg mol–1, RG ≈ 97 nm, Mw/Mn = 1.04) whose concentration was varied from dilute to more than 10c*. Whereas for dilute solutions the intensity–intensity correlation function follows a single diffusion process, it splits starting at c* to imply an additional relaxation process provided that the experimental focal area does not greatly exceed the polymer blob size. We identify the slower mode as self-diffusion and the increasingly rapid mode as correlated segment fluctuations that reflect the cooperative diffusion coefficient, Dcoop. These real-space measurements find quantitative agreement between correlation lengths inferred from dynamic measurements and those from determining the limit below which diffusion coefficients are independent of spot size. This study is considered to illustrate the potential of importing into polymer science the techniques of super-resolution imaging.Keywords: polymer dynamics; semidilute polymer solutions; super-resolution spectroscopy;

In the current issue of ACS Nano, Löbling, Haataja et al. craft polymeric nanoparticles with a hierarchy of nontrivial surface structures by combining conventional interpolyelectrolyte complexation with steric control from an uncharged copolymer block. Remarkable cylindrical and lamellar nanodomains are produced on the polyionic coronae of spherical micelles. Here, we discuss generalizing this elegant self-assembly strategy and provide speculative perspectives for its future potential for new nanomaterials.

We scrutinize three decades of probability density displacement distribution in a simple colloidal suspension with hard-sphere interactions. In this index-matched and density-matched solvent, fluorescent tracer nanoparticles diffuse among matrix particles that are eight times larger, at concentrations from dilute to concentrated, over times up to when the tracer diffuses a few times its size. Displacement distributions of tracers, Gaussian in pure solvent, broaden systematically with increasing obstacle density. The onset of non-Gaussian dynamics is seen in even modestly dilute suspensions, which traditionally would be assumed to follow classic Gaussian expectation. The findings underscore, in agreement with recent studies of more esoteric soft matter systems, the prevalence of non-Gaussian yet Fickian diffusion.Keywords: complex fluids; crowding; diffusion; hard-sphere colloids; non-Gaussian

Solutions of aqueous methylcellulose, a hydrophobically modified polymer (molecular weight ≈270 kg/mol, methyl content ≈30%), are mixed with either dilute coumarin fluorescent dye or carboxylated latex (20 nm diameter), and the tracer diffusion is contrasted as a function of temperature and polymer concentration (from dilute to 36 times the overlap concentration) in deionized water. From two-photon fluorescence correlation spectroscopy (FCS), mean-square displacement is inferred. At room temperature, which is the fluid state, we observe Fickian diffusion provided that the tracer particle size is less than the polymer mesh size, whereas tighter meshes produce subdiffusion followed by Fickian diffusion at long times. At elevated temperature, which is the gel state, subdiffusion is observed over the entire experimental time window. To quantify subdiffusion, the data are described equally well as two discrete relaxations or a stretched exponential, and the former is analyzed in detail as it is considered to be more meaningful physically. These measurements allow us to discuss the structure and degree of inhomogeneity of methylcellulose in the gel state. This industrially relevant polymer produces simple, physically meaningful diffusion patterns that we find to be repeatable, obeying systematic patterns described quantitatively in this paper.

For study of time-dependent conformation, all previous single-molecule imaging studies of polymer transport involve fluorescence labeling uniformly along the chain, which suffers from limited resolution due to the diffraction limit. Here we demonstrate the concept of submolecular single-molecule imaging with DNA chains assembled from DNA fragments such that a chain is labeled at designated spots with covalently attached fluorescent dyes and the chain backbone with dyes of different color. High density of dyes ensures good signal-to-noise ratio to localize the designated spots in real time with nanometer precision and prevents significant photobleaching for long-time tracking purposes. To demonstrate usefulness of this approach, we image electrophoretic transport of λ-DNA through agarose gels. The unexpected pattern is observed that one end of each molecule tends to stretch out in the electric field while the other end remains quiescent for some time before it snaps forward and the stretch–recoil cycle repeats. These features are neither predicted by prevailing theories of electrophoresis mechanism nor detectable by conventional whole-chain labeling methods, which demonstrate pragmatically the usefulness of modular stitching to reveal internal chain dynamics of single molecules.

Methods are described to synthesize shape-selectable, monodisperse, aqueous-stable metal–organic frameworks (MOFs) by the reaction of aluminium nitrate with benzene tricarboxylic acid in various aqueous solvent mixtures and acetic acid as the capping ligand. Environmental stability was confirmed by thermal analysis and immersion in aqueous acidic media.

Single-molecule fluorescence imaging of adsorption onto initially bare surfaces shows that polymer chains need not localize immediately after arrival. In a system optimized to present limited adsorption sites (quartz surface to which polyethylene glycol (PEG) chains adsorb from aqueous solution at pH 8.2), we find that some chains diffuse back into bulk solution and readsorb at some distance away, sometimes multiple times before they either localize at a stable position or diffuse away into bulk solution. This mechanism of surface diffusion is considerably more rapid than the classical model in which adsorbed polymers crawl on surfaces while the entire molecule remains adsorbed, suggesting the conceptual generality of a recent report ( Phys. Rev. Lett. 2013, 110, 256101) but in a new experimental system and with comparison of different chain lengths. We find the trajectories with jumps to follow a truncated Lévy distribution of step size with limiting slope −2.5, consistent with a well-defined, rapid surface diffusion coefficient over the times we observe. The broad waiting time distribution appears to reflect that polymer chains possess a broad distribution of bound fraction: the smaller the bound fraction of a given chain, the shorter the surface residence time before executing the next surface jump.Keywords: jump; polymer adsorption/desorption; single-molecule fluorescence imaging; surface diffusion; truncated Lévy distribution

We demonstrate sequential assembly of chemically patchy colloids such that their valence differs from stage to stage to produce hierarchical structures. For proof of concept, we employ ACB triblock spheres suspended in water, with the C middle band electrostatically repulsive. In the first assembly stage, only A–A hydrophobic attraction contributes, and discrete clusters form. They can be stored, but subsequently activated to allow B–B attractions, leading to higher-order assembly of clusters with one another. The growth dynamics, observed at a single particle level by fluorescence optical microscopy, obey the kinetics of stepwise polymerization, forming chains, pores, and networks. Between linked clusters, we identify three possible bond geometries, linear, triangular, and square, by an argument that is generalizable to other patchy colloid systems. This staged assembly strategy offers a promising route to fabricate colloidal assemblies bearing multiple levels of structural and functional complexity.

Monodisperse polyhedral metal–organic framework (MOF) particles up to 5 μm in size, large enough to enable in situ optical imaging of particle orientation, were synthesized by the strategy of simultaneous addition of two capping ligands with different binding strength during crystallization. Upon dispersing them in ethylene glycol and applying AC electric field, the particles facets link to form linear chains. We observe well-regulated crystal orientation not only for rhombic dodecahedra all of whose facets are equivalent, but also for truncated cubes with nondegenerate facets. After removing the electric field, chains disassemble if their facets contain even modest curvature, but remain intact if their facets are planar. This assembly strategy offers a general route to fabricate oriented polyhedral crystal arrays of potential interest for new applications and functions.

We fabricated chemically and shape-anisotropic colloids composed of silica rods coated with gold tips using a multistep process involving electric-field alignment and crystallization, microcontact printing, and selective metallization. Through direct observation, we found that these “Janus matchsticks” self-assemble into multipods (bi-, tri-, and tetrapods) of varying coordination number and patch angle in aqueous solution.

Methods for functionalizing micrometer-sized colloidal spheres with three or more zones of chemical functionality (ABA or ABC) are described. To produce ABA triblock colloids, we functionalized the north pole, south pole, and equator to produce what we call X, Y, and K functionality according to the number of allowed nearest neighbors and their spatial arrangements. These synthesis methods allowed targeting of various lattice structures whose bonding between neighboring particles in liquid suspension was visualized in situ by optical microscopy.

Building upon the observation that liposomes of zwitterionic lipids can be stabilized against fusion by the adsorption of cationic nanoparticles (Yu, Y.; Anthony, S.; Zhang, L.; Bae, S. C.; Granick, S. J. Phys. Chem. C2007, 111, 8233), we study, using single-particle fluorescence tracking, mobility in this distinctively deformable colloid system, in the volume fraction range of φ = 0.01 to 0.7. Liposome motion is diffusive and homogeneous at low volume fractions, but separable fast and slow populations emerge as the volume fraction increases beyond φ ≈ 0.45, the same volume fraction at which hard colloids with sufficiently strong attraction are known to experience gelation. This is reflected not only in scaling of the mean square displacement, but also in the step size distribution (van Hove function) measured by fluorescence imaging. The fast liposomes are observed to follow Brownian motion, and the slow ones follow anomalous diffusion characterized by a 1/3 time scaling of their mean square displacement.

We show that cationic nanoparticles encapsulated within vesicles of phosphocholine lipid can induce pearling. The dynamic process occurs as two stages: formation of tubular protrusions followed by pearling instability. The breakup into individual vesicles can be controlled by nanoparticle concentration.

Methods are described to synthesize shape-selectable, monodisperse, aqueous-stable metal–organic frameworks (MOFs) by the reaction of aluminium nitrate with benzene tricarboxylic acid in various aqueous solvent mixtures and acetic acid as the capping ligand. Environmental stability was confirmed by thermal analysis and immersion in aqueous acidic media.