Orientation Polarization Spectroscopy-Toward an Atomistic Understanding of Dielectric Relaxation Processes.

The theory of orientation polarization and dielectric relaxation was developed by P. Debye more than 100 years ago. It is based on approximating a molecule by a sphere having one or more dipole moments. By that the detailed intra- and intermolecular interactions are explicitly not taken into consideration. In this article, the principal limitations of the Debye approximation are discussed. Taking advantage of the molecular specificity of the infrared (IR) spectral range, measurements of the specific IR absorption of the stretching vibration υ(OH) (at 3370 cm-1) and the asymmetric υas(CH2) (at 2862.9 cm-1) are performed in dependence on the frequency and the strength of external electric fields and at varying temperature. The observed effects are interpreted as caused by orientation polarization of the OH and the adjacent CH2 moieties.

Molecular heterogeneities in the thermal expansivity of polyalcohols.

Density is the key quantity for nearly all the numerous theories of the (dynamic) glass transition of supercooled liquids and melts. As mean field quantity, it is used to describe correlations and heterogeneities between regions consisting of several molecules. In contrast, the question how density is created by the interactions (i.e., bonds) within a molecule and to its nearest neighbors is almost unexplored. To investigate this for the example of a homologous series of polyalcohols (glycerol, threitol, xylitol, and sorbitol), Fourier-Transform InfraRed (FTIR) spectroscopy is carried out in a wide range of temperatures from far above to far below the calorimetric glass transition Tg. This enables us to determine the potentials and hence the bond lengths of specific intramolecular and intermolecular interactions. While the former has an expansion coefficient of (∼0.1 pm/100 K) with only smooth changes, the latter shows a 30-40 times stronger response with pronounced kinks at Tg. A comparison with the overall expansion based on mass density reveals that one has to separate between strong (OH⋅⋅⋅O) and weak (CH⋅⋅⋅O) intermolecular hydrogen (H)-bridges. Despite the fact that the latter dominates glassy dynamics, their expansivity is 5 times smaller than that of the weak H-bridges. It is to be expected that such heterogeneities on intramolecular and intermolecular scales are a general phenomenon in liquids and glassy systems demonstrating especially the necessity of atomistic simulations.

Interfacial Dynamics in Supported Ultrathin Polymer Films-From the Solid to the Free Interface.

Molecular dynamics in ultrathin layers is investigated using nanostructured electrodes to perform broadband dielectric spectroscopy measurements, and by atomistic molecular dynamics simulations. Using poly(vinyl acetate) as the model system and taking advantage of access to the distribution of relaxation times in an extended temperature range above the glass transition temperature, Tg, we demonstrate that while the mean rates of the segmental relaxation remain bulklike down to 12 nm film thickness, modified molecular mobilities arise in the interfacial zones. Combining results from simulations and experiments, we show unambiguously that both the slow relaxations arising from adsorbed polymer segments and the faster modes attributed to segments in the vicinity of the free interface have non-Arrhenius temperature activation. These interfacial regions span thicknesses of ∼1.5 nm each just above the calorimetric Tg independent of molecular weight and film thickness. These deviations at interfaces are relevant for applications of polymers in adhesion, coatings, and polymer nanocomposites.

Hydrogen bonding and charge transport in a protic polymerized ionic liquid.

Hydrogen bonding and charge transport in the protic polymerized ionic liquid poly[tris(2-(2-methoxyethoxy)ethyl)ammoniumacryloxypropyl sulfonate] (PAAPS) are studied by combining Fourier transform infrared (FTIR) and broadband dielectric spectroscopy (BDS) in a wide temperature range from 170 to 300 K. While the former enables to determine precisely the formation of hydrogen bonds and other moiety-specific quantized vibrational states, the latter allows for recording the complex conductivity in a spectral range from 10-2 to 10+9 Hz. A pronounced thermal hysteresis is observed for the H-bond network formation in distinct contrast to the reversibility of the effective conductivity measured by BDS. On the basis of this finding and the fact that the conductivity changes with temperature by orders of magnitude, whereas the integrated absorbance of the N-H stretching vibration (being proportional to the number density of protons in the hydrogen bond network) changes only by a factor of 4, it is concluded that charge transport takes place predominantly due to hopping conduction assisted by glassy dynamics (dynamic glass transition assisted hopping) and is not significantly affected by the establishment of H-bonds.

Determination of the Complete Elasticity of Nephila pilipes Spider Silk.

Spider silks are remarkable materials designed by nature to have extraordinary elasticity. Their elasticity, however, remains poorly understood, as typical stress-strain experiments only allow access to the axial Young's modulus. In this work, micro-Brillouin light spectroscopy (micro-BLS), a noncontact, nondestructive technique, is utilized to probe the direction-dependent phonon propagation in the Nephila pilipes spider silk and hence solve its full elasticity. To the best of our knowledge, this is the first demonstration on the determination of the anisotropic Young's moduli, shear moduli, and Poisson's ratios of a single spider fiber. The axial and lateral Young's moduli are found to be 20.9 ± 0.8 and 9.2 ± 0.3 GPa, respectively, and the anisotropy of the Young's moduli further increases upon stretching. In contrast, the shear moduli and Poisson's ratios exhibit very weak anisotropy and are robust to stretching.

Relaxation Dynamics of Thin Matrimid 5218 Films in Organic Solvents.

Polyimides are interesting polymer materials for organic solvent nanofiltration (OSN) applications because of their high excess free volume and high chemical and temperature resistance. However, an open challenge that remains for glassy polymer materials (i.e., polyimides) is their tendency to swell in organic solvents which can lead to a loss of performance. An understanding on how swelling influences the polymer properties and performance is then of crucial importance for assessing polyimide suitability in OSN applications. Here, the combination of in situ spectroscopic ellipsometry (iSE), broadband dielectric spectroscopy (BDS), and diffuse reflectance Fourier transform infrared spectroscopy (DRIFT-FTIR) is applied to study the molecular interaction of two organic penetrants, toluene and n-hexane, with Matrimid 5218 in detail. iSE shows that slightly cross-linked Matrimid 5218 swells approximately seven times more in toluene (swelling degree ≈ 28%) compared to in n-hexane (swelling degree ≈ 4%). Combined BDS and DRIFT-FTIR results indicate that toluene interacts with the benzene ring present in the diamine via π-π interactions, while n-hexane likely fills up the excess free volume and interacts via local van der Waals interactions. This work highlights the insights into the exact nature of the molecular interactions between the penetrant and polymer that can be gained from a combination of BDS and other techniques and how these insights can be used to estimate or understand solvent-induced swelling of polymers used in OSN applications.

Charge transport and glassy dynamics in polymeric ionic liquids as reflected by their inter- and intramolecular interactions.

Polymeric ionic liquids (PILs) form a novel class of materials in which the extraordinary properties of ionic liquids (ILs) are combined with the mechanical stability of polymeric systems qualifying them for multifold applications. In the present study broadband dielectric spectroscopy (BDS), Fourier transform infrared spectroscopy (FTIR), AC-chip calorimetry (ACC) and differential scanning calorimetry (DSC) are combined in order to unravel the interplay between charge transport and glassy dynamics. Three low molecular weight ILs and their polymeric correspondents are studied with systematic variations of anions and cations. For all examined samples charge transport takes place by glassy dynamics assisted hopping conduction. In contrast to low molecular weight ILs the thermal activation of DC conductivity for the polymeric systems changes from a Vogel-Fulcher-Tammann- to an Arrhenius-dependence at a (sample specific) temperature Tσ0. This temperature has been widely discussed to coincide with the glass transition temperature Tg, a refined analysis, instead, reveals Tσ0 of all PILs under study at up to 80 K higher values. In effect, below the Tσ0 charge transport in PILs becomes more efficient - albeit on a much lower level compared to the low molecular weight pendants - indicating conduction paths along the polymer chain. This is corroborated by analysing the temperature dependence of specific IR-active vibrations showing at Tσ0 distinct changes in the spectral position and the oscillator strength, whereas other molecular units are not affected. This leads to the identification of charge transport responsive (CTR) as well as charge transport irresponsive (CTI) moieties and paves the way to a refined molecular understanding of electrical conduction in PILs.

Glassy dynamics of two poly(ethylene glycol) derivatives in the bulk and in nanometric confinement as reflected in its inter- and intra-molecular interactions.

The inter- and intra-molecular interactions as they evolve in the course of glassy solidification are studied by broadband dielectric-and Fourier-transform infrared-spectroscopy for oligomeric derivatives of poly(ethylene glycol) derivatives, namely, poly(ethylene glycol) phenyl ether acrylate and poly(ethylene glycol) dibenzoate in the bulk and under confinement in nanoporous silica having mean pore diameters 4, 6, and 8 nm, with native and silanized inner surfaces. Analyzing the spectral positions and the oscillator strengths of specific IR absorption bands and their temperature dependencies enables one to trace the changes in the intra-molecular potentials and to compare it with the dielectrically determined primarily inter-molecular dynamics. Special emphasis is given to the calorimetric glass transition temperature Tg and Tαß ≈ 1.25Tg, where characteristic changes in conformation appear, and the secondary ß-relaxation merges with the dynamic glass transition (α-relaxation). Furthermore, the impact of main chain conformations, inter- and intra-molecular hydrogen bonding, and nanometric confinement on the dynamic glass transition is unraveled.

Temperature-dependent IR-transition moment orientational analysis applied to thin supported films of poly-ε-caprolactone.

A novel experimental setup is described which enables one to carry out infrared transition moment orientational analysis (IR-TMOA) depending on temperature. By this, three dimensional molecular order parameter tensors of IR-active transition dipole moments with respect to the sample coordinate system can be determined in their thermal evolution (35 °C < T < 59 °C). As an example crystallinity and macroscopic order of poly-ε-caprolcatone are monitored. Both remain largely unaltered up to T ∼ 50 °C, above which they decrease. These reductions are explained as the melting of flat-on crystalline lamellae that make up about 34% of the crystalline material. The remaining crystallites are arranged into bulk-like, confined spherulitic structures and do not melt by more than (3 ± 3)%. Therefore, flat-on oriented lamellae are supposed to be kinetically favored by confinement during melt crystallization but are thermodynamically less stable than two-dimensionally confined bulk-like spherulites.

Foundation of the Outstanding Toughness in Biomimetic and Natural Spider Silk.

Spider dragline silk is distinguished through the highest toughness of all natural as well as artificial fiber materials. To unravel the toughness's molecular foundation and to enable manufacturing biomimetic analogues, we investigated the morphological and functional structure of recombinant fibers, which exhibit toughness similar to that of the natural template, on the molecular scale by means of vibrational spectroscopy and on the mesoscale by X-ray scattering. Whereas the former was used to identify protein secondary structures and their alignment in the natural as well as artificial silks, the latter revealed nanometer-sized crystallites on the higher structural level. Furthermore, a spectral red shift of a crystal-specific absorption band demonstrated that macroscopically applied stress is directly transferred to the molecular scale, where it is finally dissipated. Concerning this feature, both the natural as well as the biomimetic fibers are almost indistinguishable, giving rise to the toughness of both fiber materials.

Glassy dynamics of polymethylphenylsiloxane in one- and two-dimensional nanometric confinement-A comparison.

Glassy dynamics of polymethylphenylsiloxane (PMPS) is studied by broadband dielectric spectroscopy in one-dimensional (1D) and two-dimensional (2D) nanometric confinement; the former is realized in thin polymer layers having thicknesses down to 5 nm, and the latter in unidirectional (thickness 50 µm) nanopores with diameters varying between 4 and 8 nm. Based on the dielectric measurements carried out in a broad spectral range at widely varying temperatures, glassy dynamics is analyzed in detail in 1D and in 2D confinements with the following results: (i) the segmental dynamics (dynamic glass transition) of PMPS in 1D confinement down to thicknesses of 5 nm is identical to the bulk in the mean relaxation rate and the width of the relaxation time distribution function; (ii) additionally a well separated surface induced relaxation is observed, being assigned to adsorption and desorption processes of polymer segments with the solid interface; (iii) in 2D confinement with native inner pore walls, the segmental dynamics shows a confinement effect, i.e., the smaller the pores are, the faster the segmental dynamics; on silanization, this dependence on the pore diameter vanishes, but the mean relaxation rate is still faster than in 1D confinement; (iv) in a 2D confinement, a pronounced surface induced relaxation process is found, the strength of which increases with the decreasing pore diameter; it can be fully removed by silanization of the inner pore walls; (v) the surface induced relaxation depends on its spectral position only negligibly on the pore diameter; (vi) comparing 1D and 2D confinements, the segmental dynamics in the latter is by about two orders of magnitude faster. All these findings can be comprehended by considering the density of the polymer; in 1D it is assumed to be the same as in the bulk, hence the dynamic glass transition is not altered; in 2D it is reduced due to a frustration of packaging resulting in a higher free volume, as proven by ortho-positronium annihilation lifetime spectroscopy.

Nonlinear control of high-frequency phonons in spider silk.

Spider dragline silk possesses superior mechanical properties compared with synthetic polymers with similar chemical structure due to its hierarchical structure comprised of partially crystalline oriented nanofibrils. To date, silk's dynamic mechanical properties have been largely unexplored. Here we report an indirect hypersonic phononic bandgap and an anomalous dispersion of the acoustic-like branch from inelastic (Brillouin) light scattering experiments under varying applied elastic strains. We show the mechanical nonlinearity of the silk structure generates a unique region of negative group velocity, that together with the global (mechanical) anisotropy provides novel symmetry conditions for gap formation. The phononic bandgap and dispersion show strong nonlinear strain-dependent behaviour. Exploiting material nonlinearity along with tailored structural anisotropy could be a new design paradigm to access new types of dynamic behaviour.

Epitope mapping of monoclonal antibody HPT-101: a study combining dynamic force spectroscopy, ELISA and molecular dynamics simulations.

By combining enzyme-linked immunosorbent assay (ELISA) and optical tweezers-assisted dynamic force spectroscopy (DFS), we identify for the first time the binding epitope of the phosphorylation-specific monoclonal antibody (mAb) HPT-101 to the Alzheimer's disease relevant peptide tau[pThr231/pSer235] on the level of single amino acids. In particular, seven tau isoforms are synthesized by replacing binding relevant amino acids by a neutral alanine (alanine scanning). From the binding between mAb HPT-101 and the alanine-scan derivatives, we extract specific binding parameters such as bond lifetime τ0, binding length x(ts), free energy of activation ΔG (DFS) and affinity constant K(a) (ELISA, DFS). Based on these quantities, we propose criteria to identify essential, secondary and non-essential amino acids, being representative of the antibody binding epitope. The obtained results are found to be in full accord for both experimental techniques. In order to elucidate the microscopic origin of the change in binding parameters, we perform molecular dynamics (MD) simulations of the free epitope in solution for both its parent and modified form. By taking the end-to-end distance d(E-E) and the distance between the α-carbons d(C-C) of the phosphorylated residues as gauging parameters, we measure how the structure of the epitope depends on the type of substitution. In particular, whereas d(C-C) is sometimes conserved between the parent and modified form, d(E-E) strongly changes depending on the type of substitution, correlating well with the experimental data. These results are highly significant, offering a detailed microscopic picture of molecular recognition.

Infrared Transition Moment Orientational Analysis on the Structural Organization of the Distinct Molecular Subunits in Thin Layers of a High Mobility n-Type Copolymer.

The IR-based method of infrared transition moment orientational analysis (IR-TMOA) is employed to unravel molecular order in thin layers of the semiconducting polymer poly[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) (P(NDI2OD-T2)). Structure-specific vibrational bands are analyzed in dependence on polarization and inclination of the sample with respect to the optical axis. By that the molecular order parameter tensor for the respective molecular moieties with regard to the sample coordinate system is deduced. Making use of the specificity of the IR spectral range, we are able to determine separately the orientation of atomistic planes defined through the naphthalenediimide (NDI) and bithiophene (T2) units relative to the substrate, and hence, relative to each other. A pronounced solvent effect is observed: While chlorobenzene causes the T2 planes to align preferentially parallel to the substrate at an angle of 29°, using a 1:1 chloronaphthalene:xylene mixture results in a reorientation of the T2 units from a face on into an edge on arrangement. In contrast the NDI unit remains unaffected. Additionally, for both solvents evidence is observed for the aggregation of chains in accord with recently published results obtained by UV-vis absorption spectroscopy.

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids.

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphonium IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range-indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.

Glassy dynamics of poly(2-vinyl-pyridine) brushes with varying grafting density.

The molecular dynamics of poly(2-vinyl-pyridine) (P2VP) brushes is measured by Broadband Dielectric Spectroscopy (BDS) in a wide temperature (250 K to 440 K) and broad spectral (0.1 Hz to 1 MHz) range. This is realized using nanostructured, highly conductive silicon electrodes being separated by silica spacers as small as 35 nm. A "grafting-to"-method is applied to prepare the P2VP-brushes with five different grafting densities (0.030 nm(-2) to 0.117 nm(-2)), covering the "true-brush" regime with highly stretched coils and the "mushroom-to-brush" transition regime. The film thickness ranges between 1.8 to 7.1 (±0.2) nm. Two relaxations are observed, an Arrhenius-like process being attributed to fluctuations in the poly(glycidyl-methacrylate) (PGMA) linker used for the grafting reaction and the segmental dynamics (dynamic glass transition) of the P2VP brushes. The latter is characterized by a Vogel-Fulcher-Tammann dependence similar to bulk P2VP. The results can be comprehended considering the length scale on which the dynamic glass transition (≤1 nm) takes place.

Structure and Dynamics of Asymmetric Poly(styrene-b-1,4-isoprene) Diblock Copolymer under 1D and 2D Nanoconfinement.

The impact of 1- and 2-dimensional (2D) confinement on the structure and dynamics of poly(styrene-b-1,4-isoprene) P(S-b-I) diblock copolymer is investigated by a combination of Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Grazing-Incidence Small-Angle X-ray Scattering (GISAXS), and Broadband Dielectric Spectroscopy (BDS). 1D confinement is achieved by spin coating the P(S-b-I) to form nanometric thin films on silicon substrates, while in the 2D confinement, the copolymer is infiltrated into cylindrical anodized aluminum oxide (AAO) nanopores. After dissolving the AAO matrix having mean pore diameter of 150 nm, the SEM images of the exposed P(S-b-I) show straight nanorods. For the thin films, GISAXS and AFM reveal hexagonally packed cylinders of PS in a PI matrix. Three dielectrically active relaxation modes assigned to the two segmental modes of the styrene and isoprene blocks and the normal mode of the latter are studied selectively by BDS. The dynamic glass transition, related to the segmental modes of the styrene and isoprene blocks, is independent of the dimensionality and the finite sizes (down to 18 nm) of confinement, but the normal mode is influenced by both factors with 2D geometrical constraints exerting greater impact. This reflects the considerable difference in the length scales on which the two kinds of fluctuations take place.

Methods to determine the pressure dependence of the molecular order parameter in (bio)macromolecular fibres.

The experimental realization and an algorithm for analysing the pressure dependence of the molecular order parameter of specific structural moieties in (bio)macromolecular fibres are described. By employing a diamond anvil cell (DAC) the polarization-dependent IR-transmission and in parallel, using an integrated microscope, the macroscopic orientation of the fibres is determined. This enables one to separate between order and disorder at macroscopic and microscopic scales. Using the example of spider silk the pressure dependence of the molecular order parameter of alanine groups being located within nano-crystalline building blocks is deduced and found to decrease reversibly by 0.01 GPa(-1) when varying the external hydrostatic pressure between 0 and 3 GPa.

Confinement for More Space: A Larger Free Volume and Enhanced Glassy Dynamics of 2-Ethyl-1-hexanol in Nanopores.

Broadband dielectric spectroscopy and positron annihilation lifetime spectroscopy are employed to study the molecular dynamics and effective free volume of 2-ethyl-1-hexanol (2E1H) in the bulk state and when confined in unidirectional nanopores with average diameters of 4, 6, and 8 nm. Enhanced α-relaxations with decreasing pore diameters closer to the calorimetric glass-transition temperature (T(g)) correlate with the increase in the effective free volume. This indicates that the glassy dynamics of 2D constrained 2E1H is mainly controlled by density variation.

The kinetics of mutarotation in L-fucose as monitored by dielectric and infrared spectroscopy.

Fourier Transform Infrared Spectroscopy and Broadband Dielectric Spectroscopy are combined to trace kinetics of mutarotation in L-fucose. After quenching molten samples down to temperatures between T = 313 K and 328 K, the concentrations of two anomeric species change according to a simple exponential time dependence, as seen by an increase in absorbance of specific IR-vibrations. In contrast, the dielectric spectra reveal a slowing down of the structural (α-) relaxation process according to a stretched exponential time dependence (stretching exponent of 1.5 ± 0.2). The rates of change in the IR absorption for α- and ß-fucopyranose are (at T = 313 K) nearly one decade faster than that of the intermolecular interactions as measured by the shift of the α-relaxation. This reflects the fact that the α-relaxation monitors the equilibration at a mesoscopic length scale, resulting from fluctuations in the anomeric composition.