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The segmental dynamics of polymers is known to be closely related to the glass transition where the glass transition is the single most important parameter in its application. In this study, we designed an efficient and reliable experimental method to study the ensemble segmental dynamics of polymers by probing rotation of fluorescent molecules in the polymer matrix using a home-built microscope setup. The rotational dynamics of fluorescent molecules was analyzed using a fluorescence correlation method that extracts information through orthogonally polarized fluorescence images. From fluorescence intensities, autocorrelation functions (ACFs) were obtained in many areas simultaneously and by averaging several ACFs, well-defined ACF and precise experimental values were obtained from a single measurement movie. The robustness of the method and optimal experimental conditions were investigated by performing experiments with various probe concentrations, frame rates, and measurement lengths. By employing a home-built vacuum chamber, a wide temperature range was achieved, and we demonstrate the versatility and efficiency of imaging rotational FCM (fluorescence correlation microscopy) by probing segmental dynamics of different polymeric systems with glass transition temperature that differ by ≈100 K and with fragility ranging from 49 to 131. The imaging rotational FCM covers dynamics up to 4 orders of magnitude near the glass transition, and it was found that the rapidity of the stretching exponent β variation with temperature correlates with the fragility of polymers.

We induced a terpyridine moiety into a norbornene-based polymer to demonstrate its self-healing property, without an external stimulus, such as light, heat, or healing agent, using metal⁻ligand interactions. We synthesized terpyridine incorporated norbornene-based polymers using a ring-opening metathesis polymerization. The sol state of diluted polymer solutions was converted into supramolecular assembled gels, through the addition of transition metal ions (Ni 2+ , Co 2+ , Fe 2+ , and Zn 2+ ). In particular, a supramolecular complex gel with Zn 2+ , which is a metal with a lower binding affinity, demonstrated fast self-healing properties, without any additional external stimuli, and its mechanical properties were completely recovered.

We demonstrate the synthesis of poly(methyl methacrylate) (PMMA) and poly(styrene- b -methyl methacrylate) (P(S- b -MMA)) brushes on crosslinked random copolymer thin films, compositionally varied poly(styrene- r -glycidyl methacrylate) (P(S- r -GMA)), which can be further functionalized with a molecule featuring an initiator group upon crosslinking to form highly stable thin films. With careful optimizations, PMMA brushes were successfully grown from the surfaces of initiator functionalized P(S- r -GMA) via surface-initiated atom transfer radical polymerization. The grafting densities of the PMMA and P(S- b -MMA) brushes were effectively controlled to be in different density regimes by controlling the composition of P(S- r -GMA) and post-crosslinking functionalization methods. Synthesized BCP brushes were stable upon repetitive washing and thermal annealing processes even at high grafting density, highlighting that the outstanding stability of crosslinked P(S- r -GMA) thin films enables close examination of the morphology of thermally annealed P(S- b -MMA) brushes in different grafting density regimes., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Polymeric systems close to their glass transition temperature are known to exhibit heterogeneous dynamics that evolve both over time and space, comparable to the dynamics of small molecule glass formers. It remains unclear how temperature influences the degree of heterogeneous dynamics in such systems. In the following report, a fluorescent perylene dicarboximide probe molecule that reflects the full breadth of heterogeneity of the host was used to examine the temperature dependence of the dynamic heterogeneity lifetime in polystyrene at several temperatures ranging from the glass transition to 10 K above this temperature via single molecule microscopy. Contrary to prior reports, no apparent temperature dependence of time scales associated with dynamic heterogeneity was detected; indeed, the probe molecules report characteristic dynamic heterogeneity lifetimes 100-300 times the average alpha-relaxation time (τ α ) of the polystyrene host at all temperatures studied.

Fibrillar type I collagen-based hydrogels are commonly used in tissue engineering and as matrices for biophysical studies. Mechanical and structural properties of these gels are known to be governed by the conditions under which fibrillogenesis occurs, exhibiting variation as a function of protein concentration, temperature, pH, and ionic strength. Deeper understanding of how macroscopic structure affects viscoelastic properties of collagen gels over the course of fibrillogenesis provides fundamental insight into biopolymer gel properties and promises enhanced control over the properties of such gels. Here, we investigate type I collagen fibrillogenesis using confocal rheology-simultaneous confocal reflectance microscopy, confocal fluorescence microscopy, and rheology. The multimodal approach allows direct comparison of how viscoelastic properties track the structural evolution of the gel on fiber and network length scales. Quantitative assessment and comparison of each imaging modality and the simultaneously collected rheological measurements show that the presence of a system-spanning structure occurs at a time similar to rheological determinants of gelation. Although this and some rheological measures are consistent with critical gelation through percolation, additional rheological and structural properties of the gel are found to be inconsistent with this theory. This study clarifies how structure sets viscoelasticity during collagen fibrillogenesis and more broadly highlights the utility of multimodal measurements as critical test-beds for theoretical descriptions of complex systems., (Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.)

The spatial arrangement of nanoparticles (NPs) within thin polymer films may influence their properties such as the glass transition temperature. Questions regarding what may affect the spatial arrangement of NPs, however, still remain unanswered at a molecular level. In this work, we perform molecular dynamics simulations for a free-standing thin polymer film with a single NP. We find from simulations that depending on the NP size and the inter-particle interaction between the NP and polymers, one may control the spatial arrangement of the NP. When the interaction between the NP and polymers is sufficiently attractive (repulsive), the NP is likely to be placed at the center (at the surface) of the thin film in equilibrium. Interestingly, for a moderate interaction between the NP and polymers, the first-order transition occurs in the spatial arrangement of the NP as one increases the NP size: a small NP prefers the surface of the polymer film whereas a large NP prefers the center. Such a first-order transition is corroborated by calculating the free energy of the NP as a function of the position and can be understood in terms of a sixth-order Landau free energy. More interestingly, the diffusion of the NP also changes drastically due to the first-order transition in the spatial arrangement. The NP diffusion is enhanced drastically (more than expected in bulk polymer melts) as the NP is shifted to the polymer film surface.

Polymer processing techniques involving solvent vapor swelling are typically challenging to control and thus reproduce. Moreover, traditional descriptions of solvent swollen films lack microscopic detail. We describe the design and use of an apparatus that facilitates macroscopic and microscopic characterization of samples undergoing solvent vapor swelling in a controlled environment. The experimental design incorporates three critical characteristics: (1) a mass-flow controlled solvent vapor delivery system allows for precise control of the amount of solvent vapor delivered to the sample, (2) a sample prepared on a quartz crystal microbalance allows for real-time assessment of the extent of sample swelling, (3) a second sample prepared and assessed in parallel on a coverslip allows real-time fluorescence microscopy during swelling. We demonstrate that this apparatus allows for single-particle tracking, which in turn facilitates in situ monitoring of local environments within the solvent-swollen film.

The relationship between photostability and conformation of 2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene (MEH-PPV) conjugated polymers was studied via excitation polarization modulation depth (M) measurements. Upon partial photobleaching, M distributions of collapsed, highly ordered MEH-PPV molecules shifted toward lower values. Conversely, M distributions of MEH-PPV molecules with random coil conformations moved toward higher values after partial photobleaching. Monte Carlo simulations of randomly distributed dipole moments along polymer chains subjected to partial photobleaching revealed that a statistical effect leads to an increase in peak M value. Decreases in M values seen experimentally in the population of MEH-PPV molecules with high M values, however, are due to conformation-dependent photostability within single MEH-PPV polymers. We show that, while folded MEH-PPV molecules are relatively more photostable than extended MEH-PPV molecules in an ensemble, extended portions of particular molecules are more photostable than folded domains within single MEH-PPV molecules.

The concept of dynamic heterogeneity and the picture of the supercooled liquid as a mosaic of environments with distinct dynamics that interchange in time have been invoked to explain the nonexponential relaxations measured in these systems. The spatial extent and temporal persistence of these regions of distinct dynamics have remained challenging to identify. Here, single-molecule fluorescence measurements using a probe similar in size and mobility to the host o-terphenyl unambiguously reveal exponential relaxations distributed in time and space and directly demonstrate ergodicity of the system down to the glass transition temperature. In the temperature range probed, at least 200 times the structural relaxation time of the host is required to recover ensemble-averaged relaxation at every spatial region in the system.

To thoroughly elucidate how molecular conformation and photophysical properties of conjugated polymers (CPs) are related requires simultaneous probing of both. Previous efforts used fluorescence imaging with one nanometer accuracy (FIONA) to image CPs, which allowed simultaneous estimation of molecular conformation and probing of fluorescence intensity decay. We show that calculating the molecular radius of gyration for putative folded and unfolded poly(2-methoxy-5-(2'-ethylhexyloxy)1,4-phenylenevinylene) (MEH-PPV) molecules using FIONA underestimates molecular extension by averaging over emitters during localization. In contrast, employing algorithms based on single molecule high resolution imaging with photobleaching (SHRImP), including an approach we term all-frames SHRImP, allows localization of individual emitters. SHRImP processing corroborates that compact MEH-PPV molecules have distinct photophysical properties from extended ones. Estimated radii of gyration for isolated 168 kDa MEH-PPV molecules immobilized in polystyrene and exhibiting either stepwise or continuous intensity decays are found to be 12.6 and 25.3 nm, respectively, while the distance between exciton recombination sites is estimated to be ∼10 nm independent of molecular conformation.

Monitoring single molecule probe rotations is an increasingly common approach to studying dynamics of complex systems, including supercooled liquids. Even with advances in fluorophore design and detector sensitivity, such measurements typically exhibit low signal to noise and signal to background ratios. Here, we simulated and analyzed orthogonally decomposed fluorescence signals of single molecules undergoing rotational diffusion in a manner that mimics experimentally collected data of probes in small molecule supercooled liquids. The effects of noise, background, and trajectory length were explicitly considered, as were the effects of data processing approaches that may limit the impact of noise and background on assessment of environmental dynamics. In many cases, data treatment that attempts to remove noise and background were found to be deleterious. However, for short trajectories below a critical signal to background threshold, a thresholding approach that successfully removed data points associated with noise and spared those associated with signal allowed for assessment of environmental dynamics that was as accurate and precise as would be achieved in the absence of noise.

Crystal growth kinetics and liquid dynamics of 1,2-diphenylcyclopentene (DPCP) and 1,2-diphenylcyclohexene (DPCH) were characterized by optical microscopy and dielectric spectroscopy. These two molecules are structurally homologous and dynamically similar to the well-studied glassformer ortho-terphenyl (OTP). In the supercooled liquid states of DPCP and DPCH, the kinetic component of crystal growth ukin has a power law relationship with the primary structural relaxation time τα, ukin [proportionality] τα(–ξ) (ξ ≈ 0.7), similar to OTP and other fragile liquids. Near the glass transition temperature (Tg), both DPCP and DPCH develop much faster crystal growth via the so-called GC (glass to crystal) mode, again similar to the behavior of OTP. We find that the α-relaxation process apparently controls the onset of GC growth, with GC growth possible only at sufficiently low fluidity. These results support the view that GC crystal growth can only occur in systems where the liquid and crystal exhibit similar local packing arrangements.

Much of the interesting behavior that has been observed in supercooled liquids appears to be related to dynamic heterogeneity, the presence of distinct dynamic environments - with no apparent underlying structural basis - in these systems. To most directly interrogate these environments, proposed to span regions just a few nanometers across, molecular length scale probes are required. Single molecule fluorescent microscopy was introduced to the field a decade ago and has provided strong evidence of dynamic heterogeneity in supercooled systems. However, only more recently has the full set of challenges associated with interpreting results of these experiments been described. With a fuller understanding of these challenges in hand, single molecule measurements can be employed to provide a more precise picture of dynamic heterogeneity in supercooled liquids and other complex systems. In this tutorial review, experimental and data analysis details are presented for the most commonly employed single molecule approach to studying supercooled liquids, the measurement of rotational dynamics of single molecule probes. Guidance is provided in experimental set-up and probe selection, with a focus on choices that affect data interpretation and probe sensitivity to dynamic heterogeneity.

A photobleaching method was used to measure the reorientation of dilute probes in liquid o-terphenyl near a crystal growth front. Near the glass-transition temperature Tg, mobility in the supercooled liquid was enhanced within ∼10 μm of the crystal growth front, by as much as a factor of 4. This enhanced mobility appears to be caused by tension created in the sample as a result of the density difference between the supercooled liquid and crystal. The maximum observed mobility enhancement corresponds to a tension of about -8 MPa, close to the cavitation limit for liquid o-terphenyl. Whereas the observed mobility near the growing crystal is not large enough to explain the extraordinary fast crystal growth observed near Tg in o-terphenyl and some other low-molecular-weight glassformers, these observations suggest that cavitation or fracture plays a key role in releasing tension and allowing fast crystal growth to occur at a steady rate.

An optical photobleaching technique has been used to measure the reorientation of dilute probes in freestanding polystyrene films as thin as 14 nm. Temperature-ramping and isothermal anisotropy measurements reveal the existence of two subsets of probe molecules with different dynamics. While the slow subset shows bulk-like dynamics, the more mobile subset reorients within a few hundred seconds even at T(g,DSC) - 25 K (T(g,DSC) is the glass transition temperature of bulk polystyrene). At T(g,DSC) - 5 K, the mobility of these two subsets differs by 4 orders of magnitude. These data are interpreted as indicating the presence of a high-mobility layer at the film surface whose thickness is independent of polymer molecular weight and total film thickness. The thickness of the mobile surface layer increases with temperature and equals 7 nm at T(g,DSC).

A temperature-ramping anisotropy measurement is introduced as an efficient way to study molecular motion in polymer glasses. For these experiments, fluorescent molecules were dispersed in the polymer glass and the reorientation of these dyes was used as a probe of segmental dynamics. For thick samples of polystyrene, poly (4-tert-butyl styrene), and poly(2-vinyl pyridine), temperature-ramping anisotropy measurements have a shape similar to differential scanning calorimetry measurements and nearly the same transition temperature. We present results using different fluorescent molecules and different temperature-ramping rates; such experiments show potential for accessing slow molecular motions considerably below T(g). Temperature-ramping anisotropy measurements were performed on freestanding poly (4-tert-butyl styrene) films of varying thicknesses. The anisotropy decay of a 22 nm film was shifted about 12 K lower in temperature as compared to a bulk sample.

When sufficient force is applied to a glassy polymer, it begins to deform through movement of the polymer chains. We used an optical photobleaching technique to quantitatively measure changes in molecular mobility during the active deformation of a polymer glass [poly(methyl methacrylate)]. Segmental mobility increases by up to a factor of 1000 during uniaxial tensile creep. Although the Eyring model can describe the increase in mobility at low stress, it fails to describe mobility after flow onset. In this regime, mobility is strongly accelerated and the distribution of relaxation times narrows substantially, indicating a more homogeneous ensemble of local environments. At even larger stresses, in the strain-hardening regime, mobility decreases with increasing stress. Consistent with the view that stress-induced mobility allows plastic flow in polymer glasses, we observed a strong correlation between strain rate and segmental mobility during creep.

The reorientation of dye molecules can be used to monitor the segmental dynamics of a polymer melt. We utilize this technique to measure stress-induced mobility in a lightly cross-linked poly(methyl methacrylate) (PMMA) glass during tensile creep deformation. At 377 K (18 K below the glass transition temperature Tg), the mobility increased by a factor of 100 during deformation with a stress of 20 MPa. Generally, the mobility increased as the stress, strain, and strain rate increased. After removing the stress, we observed that the enhanced mobility slowly disappeared during strain recovery. At 377 K, when the stress is lower than 11 MPa, almost no mobility enhancement was observed. Once the stress crossed this threshold value, the mobility dramatically increased.

A new type of disposable amperometric sensor is devised by screen printing thick-film electrodes directly on a porous nitrocellulose (NC) strip. The chromatographic NC strip is then utilized to introduce various sample pretreatment layers. As a preliminary application, a glucose biosensor based on hydrogen peroxide detection is constructed by immobilizing glucose oxidase (GOx) on the NC electrode strip and by formulating a strong oxidation layer (i.e., PbO2) at the sample loading area, placed below the GOx reaction band. The screen-printed PbO2 paste serves as a sample pretreatment layer that removes interference by its strong oxidizing ability. Samples applied are carried chromatographically, via the PbO2 paste, to the GOx layer, and glucose is catalyzed to liberate hydrogen peroxide, which is then detected at the electrode surface. The proposed NC/PbO2 strip sensor is shown to be virtually insusceptible to interfering species such as acetaminophen and ascorbic and uric acids and to exhibit good performance, in terms of the sensor-to-sensor reproducibility (standard deviation, +/-0.026 - +/-0.086 microA), the sensitivity (slope, -0.183 microA/mM), and the linearity (correlation coefficient, 0.994 in the range of 0-10 mM).