Dynamics and kinetics of structure formation in molecularly tethered fluorocarbon/hydrocarbon amphiphiles.

Biphasic fluorocarbon/hydrocarbon amphiphiles tethered to cores at distances commensurate with their packing requirement can provide thermodynamic pathways toward equilibrium. This contrasts with the analogous semifluorinated alkanes. The dynamics of a fluorous biphasic hexa(3,5-substituted-phenyl)benzene (HPB) is studied with dielectric spectroscopy as a function of temperature and pressure in comparison to the parent biphasic diphenylacetylene (DPA). Dielectric spectroscopy is a sensitive probe of the fluorocarbon environment through the end C-F dipole. Four dielectrically active processes were observed that associate with the CF(3) environment within the different phases (isotropic, liquid-like lamellar, solid lamellar, glassy state). Pressure facilitates the construction of the equilibrium phase diagram. The kinetic pathways to fluorocarbon organization are explored by pressure-jump experiments. A highly cooperative process was found that is atypical of a nucleation and growth process expected for first-order transitions.

Fast and slow dynamics in a discotic liquid crystal with regions of columnar order and disorder.

Aromatic disk-shaped molecules tend to self-organize into a herringbone packing where the disks are inclined at angles ±Î¸ with respect to the axis of the column. In discotic liquid crystals this can introduce defects between stacks of limited length. In a C(3)-symmetric hexa-peri-hexabenzocoronene, solid-state NMR, x-ray scattering, and rheology identifies such a packing with θ=43° and stacks of about seven disks. Disordered regions containing defects fill the space in between the ordered stacks. Biaxial intra- and intercolumnar dynamics differing by eight decades are identified.

Does Brillouin light scattering probe the primary glass transition process at temperatures well above glass transition?

The primary alpha-relaxation time (tau(alpha)) for molecular and polymeric glass formers probed by dielectric spectroscopy and two light scattering techniques (depolarized light scattering and photon correlation spectroscopy) relates to the decay of the torsional autocorrelation function computed by molecular dynamics simulation. It is well known that Brillouin light scattering spectroscopy (BLS) operating in gigahertz frequencies probes a fast (10-100 ps) relaxation of the longitudinal modulus M*. The characteristic relaxation time, irrespective of the fitting procedure, is faster than the alpha-relaxation which obeys the non-Arrhenius Vogel-Fulcher-Tammann equation. Albeit, this has been noticed, it remains a puzzling finding in glass forming systems. The available knowledge is based only on temperature dependent BLS experiments performed, however, at a single wave vector (frequency). Using a new BLS spectrometer, we studied the phonon dispersion at gigahertz frequencies in molecular [o-terphenyl (OTP)] and polymeric [polyisoprene (PI) and polypropylene (PP)] glass formers. We found that the hypersonic dispersion does relate to the glass transition dynamics but the disparity between the BLS-relaxation times and tau(alpha) is system dependent. In PI and PP, the former is more than one order of magnitude faster than tau(alpha), whereas the two relaxation times become comparable in the case of OTP. The difference between the two relaxation times appears to relate to the "breadth" of the relaxation time distribution function. In OTP the alpha-relaxation process assumes a virtually single exponential decay at high temperatures well above the glass transition temperature, in clear contrast with the case of the amorphous bulk polymers.

Effect of chain topology on the self-organization and dynamics of block copolypeptides: from diblock copolymers to stars.

The effect of chain topology on (i) the peptide secondary structure, (ii) the nanophase self-assembly, and (iii) the local segmental and global peptide relaxations has been studied in a series of model diblock and 3-arm star copolypeptides of poly(epsilon-carbobenzyloxy-L-lysine) (PZLL) and poly(gamma-benzyl-L-glutamate) (PBLG) with PZLL forming the core. Diblock copolypeptides are nanophase separated with PBLG and PZLL domains comprising alpha-helices packed in a hexagonal lattice. Star copolypeptides are only weakly phase separated, comprising PBLG and PZLL alpha-helices in a pseudohexagonal lattice. Phase mixing has profound consequences on the local and global dynamics. The relaxation of the peptide secondary structure speeds up, and the helix persistence length is further reduced in the stars, signifying an increased concentration of helical defects.

Thermodynamic, structural, and nanomechanical properties of a fluorous biphasic material.

The dynamics of the amphiphilic semifluorinated F(CF2)12(CH2)12H (F12H12) alkane that undergoes two condensed phase transitions have been investigated by Brillouin light spectroscopy, shear rheometry, small- (SAXS) and wide-angle (WAXS) X-ray scattering, and thermodynamic PVT measurements. The solid (I)-solid (II) transition (Ts) is marked by a stronger temperature dependence of the sound velocity in phase II and by a 2 orders of magnitude drop of the shear modulus. Between the Ts and the melting transition (Tm), the presence of two phonons implies a coexistence of solid (II) and amorphous (liquid) regions in the submicrometer range at thermal equilibrium as revealed by the SAXS pattern of a single reflection superimposed on a very broad amorphous halo. This intriguing finding of a transient, very slow (over 10 h) solid/liquid coexistence within phase II is rationalized by a two-stage mechanism for melting of the smectic phase (II) of F12H12. A refinement of the known packing motifs for the two solid-state structures is proposed.

Origin of the complex molecular dynamics in functionalized discotic liquid crystals.

The molecular dynamics of three dipole functionalized hexa-peri-hexabenzocoronenes have been studied using site-specific NMR techniques and dielectric spectroscopy as a function of temperature and pressure. These probes (i) suggest that the thermodynamic state completely controls the dynamic response, (ii) clarify the origin of two dynamic processes associated with the presence of two glass temperatures, and (iii) provide the first phase diagram for substances of this kind.

Diffusion and conformation of peptide-functionalized polyphenylene dendrimers studied by fluorescence correlation and 13C NMR spectroscopy.

We report on the combined use of fluorescence correlation spectroscopy (FCS) and 1H and 13C NMR spectroscopy to detect the size and type of peptide secondary structures in a series of poly-Z-L-lysine functionalized polyphenylene dendrimers bearing the fluorescent perylenediimide core in solution. In dilute solution, the size of the molecule as detected from FCS and 1H NMR diffusion measurements matches nicely. We show that FCS is a sensitive probe of the core size as well as of the change in the peptide secondary structure. However, FCS is less sensitive to functionality. A change in the peptide secondary conformation from beta-sheets to alpha-helices detected by 13C NMR spectroscopy gives rise to a steep increase in the hydrodynamic radii for number of residues n > or = 16. Nevertheless, helices are objects of low persistence.

Surface-functionalized nanoparticles with liquid-like behavior: the role of the constituent components.

Ionically modified silica nanoparticles with large counter anions (sulfonate, isostearate) at two silica volume fractions (13 and 27%) form a viscous fluid and a glass but not crystalline solids. Dielectric spectroscopy, Brillouin scattering and shear rheometry were employed to investigate these new nanoparticle-based fluids. The glass transition temperature and hence the local dynamics are governed by the large counter anions, whereas the flow properties can be controlled by the spatial correlation between the nanoparticles, e.g. by tuning the volume fraction of hard cores and local interactions between segments in the soft corona. Liquid-like ordering of the cores was revealed by X-ray scattering and found to influence significantly the macroscopic flow properties of these salts.

Thermodynamics and rheology of cycloolefin copolymers.

Cycloolefin copolymers of ethylene and norbornene, with norbornene content in the range from 36 to 62 mol %, were studied with respect to the thermal, thermodynamic, and rheological properties using differential scanning calorimetry, pressure-volume-temperature, and dynamic mechanical measurements. All copolymers obey the principle of time-temperature superposition, i.e., they can be considered as thermorheologically simple except for a temperature range in the vicinity of T(g). Despite this, the results on (i) the ratio of activation energies E(V)(*)/H(*) used to quantify the origin of the liquid-to-glass transition, (ii) the pressure coefficient of the glass temperature T(g)(P), and (iii) the dynamic fragility m suggest increasing dynamic heterogeneity with increasing norbornene content that is driven by the structural heterogeneity along the backbone.

The role of temperature and density on the glass-transition dynamics of glass formers.

A correlation between the monomeric volume and the dynamic quantity E*(V)/H*, used to provide a quantitative measure of the role of temperature and density on the dynamics, is demonstrated for a series of polymers and glass-forming liquids. We show that monomeric volume and local packing play a key role in controlling the value of this ratio and thus the dynamics associated with the glass temperature.

Thermodynamic confinement and alpha-helix persistence length in poly(gamma-benzyl-L-glutamate)-b-poly(dimethyl siloxane)-b-poly(gamma-benzyl-L-glutamate) triblock copolymers.

The structure and the associated dynamics of a series of poly(gamma-benzyl-L-glutamate)-b-poly(dimethyl siloxane)-b-poly(gamma-benzyl-L-glutamate) (PBLG-b-PDMS-b-PBLG) triblock copolymers were investigated using small- and wide-angle X-ray scattering, NMR, transmission electron microscopy, and dielectric spectroscopy, respectively. The structural analysis revealed phase separation in the case of the longer blocks with defected alpha-helical segments embedded within the block copolymer nanodomains. The alpha-helical persistence length was found to depend on the degree of segregation; thermodynamic confinement and chain stretching results in the partial annihilation of helical defects.

Self-assembly of pODMA-b-ptBA-b-pODMA triblock copolymers in bulk and on surfaces. A quantitative SAXS/AFM comparison.

The phase state of a series of poly(n-octadecyl methacrylate)-b-poly(tert-butyl acrylate)-b-poly(n-octadecyl methacrylate) (pODMA-b-ptBA-b-pODMA) triblock copolymers, synthesized through atom transfer radical polymerization, has been investigated in bulk and on surfaces using small-angle X-ray scattering and atomic force microscopy, respectively. The mean-field theory was employed to construct the bulk phase diagram. Excellent agreement was found between the bulk and surface morphologies as well as for the domain spacing (domain spacing scaled as d approximately equal to N(0.64)), suggesting that the strong polymer-polymer interactions in bulk are also the dominant interactions on surfaces.

Pressure-enhanced dynamic heterogeneity in block copolymers of poly(methyl vinyl ether) and poly(isobutyl vinyl ether).

The static structure factor and associated dynamics have been investigated in a series of block copolymers of poly(methyl vinyl ether) (PMVE) and poly(isobutyl vinyl ether) (PiBVE) using x-ray scattering and dielectric spectroscopy (DS). The origin of the dynamic arrest at the glass temperature (T(g)) of PiBVE has been explored by temperature- and pressure-dependent DS and pressure-volume-temperature measurements. Both temperature and volume are responsible for the segmental dynamics but temperature has a stronger effect. The copolymers display a minimal dynamic asymmetry (Delta T(g) approximately 7 K), nevertheless, are spatially and dynamically heterogeneous. Increasing pressure, unlike temperature, enhances the dynamic heterogeneity. This effect originates from the distinctly different pressure sensitivities of the homopolymers and can be traced back to differences in local packing.

Nanodomain-induced chain folding in poly(gamma-benzyl-L-glutamate)-b-polyglycine diblock copolymers.

We report on the self-assembly mechanism and dynamics in a series of poly(gamma-benzyl-l-glutamate)-b-poly(glycine) (PBLG-b-PGly) diblock copolymers within the composition range 0.67 < or = f(PBLG) < or = 0.97 and the temperature (T) range 303 < T < 433 K. Small- and wide-angle X-ray scattering, (13)C NMR, and differential scanning calorimetry are used for the structure investigation coupled with dielectric spectroscopy for both the peptide secondary structure and the associated dynamics. These techniques provide not only the nanophase morphology but also the type and persistence of peptide secondary structures. The thermodynamic confinement of the blocks within the nanodomains and the disparity in their packing efficiency results in multiple chain folding of the PGly secondary structure that effectively stabilize a lamellar morphology for high f(PBLG). Nanoscale confinement proves to be important in controlling the persistence length of secondary peptide motifs.

"Glass transition" in peptides: temperature and pressure effects.

We report on the origin of the liquid-to-glass transition in a series of oligopeptides of gamma-benzyl-L-glutamate up to the polymer (PBLG), and in Poly-Z-L-lysine (PZLL) and Polyglycine (PGly) using dielectric spectroscopy as a function of temperature and pressure. We show that temperature is the dominant control variable of the dynamics associated with the peptidic "glass transition." This is an intrinsic feature of the peptide dynamics, irrespective of the type of amino acid and of the peptide secondary structure. The influence of the type of secondary structure (alpha helix vs beta sheet) on the liquid-to-glass dynamics is discussed.

Molecular dynamics of oligofluorenes: a dielectric spectroscopy investigation.

The molecular dynamics were investigated in a series of "defect-free" oligofluorenes up to the polymer by dielectric spectroscopy (DS). The method is very sensitive to the presence of keto "defects" that when incorporated on the backbone give rise to poor optical and electronic properties. Two dielectrically active processes were found (beta and alpha process). The latter process (alpha) displays strongly temperature dependent relaxation times and temperature- and molecular weight-dependent spectral broadening associated with intramolecular correlations. The glass temperature (Tg) obeys the Fox-Flory equation and the polymer Tg is obtained by DS at 332 K. The effective dipole moment associated with the alpha process is 0.27 +/- 0.03 D.

Effects of temperature and pressure on the stability and mobility of phases in rigid rod poly (p-phenylenes).

The structure and the associated dynamics have been investigated in melts of hairy-rod macromolecules composed from a poly(p-phenylene) backbone with sulfonate ester and dodecyl side chains. For the structure investigation, polarizing optical microscopy, differential scanning calorimetry, pressure-volume-temperature, and wide-angle x-ray scattering have been employed whereas for the dynamics dielectric spectroscopy as a function of temperature and pressure was used. Based on the combined information from structure and dynamics the relaxation mechanisms were identified and the origin of the glass transition has been discussed in terms of insufficient thermal energy rather than insufficient free volume. The relevant phase diagram has been constructed and the stability and mobility of phases is discussed.

Self-assembly and dynamics of poly(gamma-benzyl-l-glutamate) peptides.

The structure and the associated dynamics have been investigated in a series of oligopeptides of gamma-benzyl-l-glutamate using DSC, WAXS, FTIR, NMR and dielectric spectroscopy, and rheology, respectively. The peptides with degrees of polymerization below 18 are mixtures of a lamellar assembly of beta sheets and of columnar hexagonal arrangement of alpha helices, whereas for longer chains, the intramolecular hydrogen bonds stabilize only the alpha-helical conformations. Multiple dielectrically active processes were found. Starting from low temperatures, the two Arrhenius processes (gamma and beta), with apparent activation energies of 20.6 and 50.2 kJ/mol, respectively, associate with the local relaxation of the side-chain methylene units (gamma process) and with more cooperative motions of the side chain dipoles sensitive to the 7/2 helical packing (beta process). The glass transition is manifested in the thermal properties with a step in the heat capacity and with an intense dielectric process bearing characteristics (molecular weight dependence, temperature dependence of relaxation times) known from amorphous polymers. Based on these findings, the alpha process is attributed to the relaxation of amorphous segments located between and at the end of helically ordered segments. Two slower processes were identified with opposite molecular weight dependence. The weak intermediate mode with an M2 molecular weight dependence of the characteristic relaxation times suggests amorphous-like chains, whereas the strong slower process originates from the loss of dipole orientational capacity caused by structural defects and reflects the migration of helical sequences along the chains. This identifies the helices as structures extending over rather short fragments of chains (i.e., of low persistence length). The viscoelastic response indicated that the structural defects arise from locally aggregated chains that inhibit the flow of oligopeptides.

Phase diagram of poly(methyl-p-tolyl-siloxane): a temperature- and pressure-dependent dielectric spectroscopy investigation.

The dynamics of poly(methyl-p-tolyl-siloxane) (PMpTS) have been studied as a function of temperature (in the range from 143 to 413 K), pressure (0.1-300 MPa), frequency (10(-2)-10(6) Hz), and molecular weight. Independent pressure-volume-temperature (PVT) measurements (for temperatures in the range from 293 to 393 K and for pressures in the range from 10 to 200 MPa) allowed calculation of the relevant thermodynamic parameters. Two dielectrically active channels of relaxation were found, one in the glassy state reflecting a localized motion of the substituted phenyl ring and one at higher temperatures reflecting the usual segmental (alpha) relaxation. In PMpTS, there are two dominant control variables; both density and temperature have a strong influence on the segmental dynamics. The PVT results allowed us to follow distinct thermodynamic (T,P) paths resulting in states bearing the same density. These isodensity states are characterized by an apparent activation energy (Q(V)) that is not very different from the corresponding activation energy under isobaric conditions (Q(V)/Q(P) approximately 0.55) reflecting the importance of thermal effects. At temperatures above the glass temperature (T(g)), strong orientation correlations exist above some critical pressure that depends on temperature. This state extends from T(g) up to 1.08 T(g) and separates a normal liquid at higher temperatures from an oriented liquid at lower temperatures. Using the "phase diagram" we discuss separately the influence of the temperature and density on the PMpTS dynamics.