Segmental and Chain Dynamics of Polyisoprene-Based Model Vitrimers.

Polymer vitrimers are a new class of materials that combine the advantages of thermoplastics and thermosets. This is due to the dynamic nature of the chemical bonds linking different chains. However, how this property affects the polymer dynamics at different length scales is still an open question. Here, we investigate the dynamics of model vitrimers based on well-defined polyisoprene (PI) chains using broadband dielectric spectroscopy. In this way, we study the polymer dynamics from the segmental to the whole chain scale, taking advantage of the fact that PI belongs to the class of molecules that exhibit a net dipole moment associated with the end-to-end vector. Three distinct relaxation phenomena are identified. The fastest relaxation is attributed to the segmental PI dynamics with a small influence of the cross-linking. An intermediate relaxation attributed to the dipolar character of the cross-linker is also observed. The slower identified relaxation component, corresponding to limited fluctuations of the end-to-end PI chains, is found to be determined by the dynamics of the clusters formed by the cross-linkers with an average time scale orders of magnitude faster than that of the terminal relaxation as inferred from the viscous flow.

Microscopic Evidence for the Topological Transition in Model Vitrimers.

In addition to the glass transition, vitrimers undergo a topological transition from viscoelastic liquid to viscoelastic solid behavior when the network rearrangements facilitated by dynamic bond exchange reactions freeze. The microscopic observation of this transition is elusive. Model polyisoprene vitrimers based on imine dynamic covalent bonds were synthesized by reaction of α,ω-dialdehyde-functionalized polyisoprenes and a tris(2-aminoethyl)amine. In these dynamic networks nanophase separation of polymer and reactive groups leads to the emergence of a relevant length scale characteristic for the network structure. We exploited the scattering sensitivity to structural features at different length scales to determine how dynamical and topological arrests affect correlations at segmental and network levels. Chains expand obeying the same expansion coefficient throughout the entire viscoelastic region, i.e., both in the elastomeric regime and in the liquid regime. The onset of liquid-like behavior is only apparent at the mesoscale, where the scattering reveals the reorganization of the network triggered by bond exchange events. The such determined "microscopic" topological transition temperature is compared with the outcome of "conventional" methods, namely viscosimetry and differential scanning calorimetry. We show that using proper thermal (aging-like) protocols, this transition is also nicely revealed by the latter.

Molecular Mobility of Polymers at the Melting Transition.

Melting of crystals is an archetypical first order phase transition. Albeit extensive efforts, the molecular origin of this process in polymers is still not clear. Experiments are complicated by the tremendous change in mechanical properties and the occurrence of parasitic phenomena masking the genuine material response. Here, we present an experimental procedure permitting to circumvent these issues by investigating the dielectric response of thin polymer films. Extensive measurements on several commercially available semicrystalline polymers allowed us to identify a genuine molecular process associated with the newly formed liquid phase. In line with recent observations of amorphous polymer melts, we show this mechanism─known as the slow Arrhenius process (SAP)─involves time scales longer than those characteristics of segmental mobility and has the same energy barrier of the flow of the melt.

Self-propelling colloids with finite state dynamics.

Endowing materials with the ability to sense, adapt, and respond to stimuli holds the key to a progress leap in autonomous systems. In spite of the growing success of macroscopic soft robotic devices, transferring these concepts to the microscale presents several challenges connected to the lack of suitable fabrication and design techniques and of internal response schemes that connect the materials' properties to the function of the active units. Here, we realize self-propelling colloidal clusters which possess a finite number of internal states, which define their motility and which are connected by reversible transitions. We produce these units via capillary assembly combining hard polystyrene colloids with two different types of thermoresponsive microgels. The clusters, actuated by spatially uniform AC electric fields, adapt their shape and dielectric properties, and consequently their propulsion, via reversible temperature-induced transitions controlled by light. The different transition temperatures for the two microgels enable three distinct dynamical states corresponding to three illumination intensity levels. The sequential reconfiguration of the microgels affects the velocity and shape of the active trajectories according to a pathway defined by tailoring the clusters' geometry during assembly. The demonstration of these simple systems indicates an exciting route toward building more complex units with broader reconfiguration schemes and multiple responses as a step forward in the pursuit of adaptive autonomous systems at the colloidal scale.

Characterization of ESBL-producing Escherichia spp. and report of an mcr-1 colistin-resistance Escherichia fergusonni strain from minced meat in Pamplona, Colombia.

Foods of animal origin are increasingly considered a source of extended spectrum ß-lactamase (ESBL) producing bacteria which can disseminate throughout the food chain and become a health concern for humans. This work aimed to evaluate the occurrence of ESBL-producing Escherichia coli in 100 retail minced meat samples taken in markets in Pamplona, Colombia. A total of 19 ESBL-producing isolates were obtained, 18 identified as E. coli and one as E. fergusonii. Fifteen isolates (78.9 %) carried blaCTX-M and blaTEM genes, one (5.2 %) blaSHV and blaTEM genes, one isolate (5.2 %) carried blaCTX-M and one (5.2 %) blaSHV alone. The majority of CTX-M-positive E. coli isolates carried the blaCTX-M-15 gene (13 isolates), being the blaCTX-M-9, blaCTX-M-2, and blaCTX-M-8 (one isolate each) also detected. Two SHV-positive isolates presented the blaSHV-5 and blaSHV-12 allele. The isolate identified as E. fergusonii was positive for blaCTX-M-65 gene and mcr-1 gene. Sixteen isolates (84.2 %) belonged to phylogroups A and B1 and grouped together in the phylogenetic tree obtained by MLST; phylogroups E and F were also detected. Transfer of ESBL resistance was demonstrated for the E. fergusonii isolate. Whole genome sequencing of this isolate revealed the presence of plasmids carrying additional resistance genes. This investigation showed the high prevalence of ESBL-producing E. coli in retail samples of minced meat. Also, the isolation of a strain of E. fergusonii is an additional concern, as some resistance genes are located in mobile elements, which can be transmitted to other bacteria. These evidences support the increasing public health concern considering the spreading of resistance genes through the food chain.

Microscopic versus Macroscopic Glass Transitions and Relevant Length Scales in Mixtures of Industrial Interest.

We have combined X-ray diffraction, neutron diffraction with polarization analysis, small-angle neutron scattering (SANS), neutron elastic fixed window scans (EFWS), and differential scanning calorimetry (DSC) to investigate polymeric blends of industrial interest composed by isotopically labeled styrene-butadiene rubber (SBR) and polystyrene (PS) oligomers of size smaller than the Kuhn length. The EFWS are sensitive to the onset of liquid-like motions across the calorimetric glass transition, allowing the selective determination of the "microscopic" effective glass transitions of the components. These are compared with the "macroscopic" counterparts disentangled by the analysis of the DSC results in terms of a model based on the effects of thermally driven concentration fluctuations and self-concentration. At the microscopic level, the mixtures are dynamically heterogeneous for blends with intermediate concentrations or rich in PS, while the sample with highest content of the fast SBR component looks as dynamically homogeneous. Moreover, the combination of SANS and DSC has allowed determining the relevant length scale for the α-relaxation through its loss of equilibrium to be ≈30 Å. This is compared with the different characteristic length scales that can be identified in these complex mixtures from structural, thermodynamical, and dynamical points of view because of the combined approach followed. We also discuss the sources of the non-Gaussian effects observed for the atomic displacements and the applicability of a Lindemann-like criterion in these materials.

Disentangling the Calorimetric Glass-Transition Trace in Polymer/Oligomer Mixtures from the Modeling of Dielectric Relaxation and the Input of Small-Angle Neutron Scattering.

We have disentangled the contributions to the glass transition as observed by differential scanning calorimetry (DSC) on simplified systems of industrial interest consisting of blends of styrene-butadiene rubber (SBR) and polystyrene (PS) oligomer. To do this, we have started from a model previously proposed to describe the effects of blending on the equilibrium dynamics of the α-relaxation as monitored by broadband dielectric spectroscopy (BDS). This model is based on the combination of self-concentration and thermally driven concentration fluctuations (TCFs). Considering the direct insight of small-angle neutron scattering on TCFs, blending effects on the α-relaxation can be fully accounted for by using only three free parameters: the self-concentration of the components φself SBR and φself PS) and the relevant length scale of segmental relaxation, 2R c. Their values were determined from the analysis of the BDS results on these samples, being that obtained for 2R c ≈ 25Å in the range usually reported for this magnitude in glass-forming systems. Using a similar approach, the distinct contributions to the DSC experiments were evaluated by imposing the dynamical information deduced from BDS and connecting the component segmental dynamics in the blend above the glass-transition temperature T g (at equilibrium) and the way the equilibrium is lost when cooling toward the glassy state. This connection was made through the α-relaxation characteristic time of each component at T g, τg. The agreement of such constructed curves with the experimental DSC results is excellent just assuming that τg is not affected by blending.

Fabrication and nanoscale properties of PEDOT:PSS conducting polymer nanospheres.

Electrically conducting nanospheres of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) with tailored size were prepared using a solvent displacement technique. To fabricate these nanostructures, dried PEDOT:PSS was dissolved in ethylene glycol (EG) and the solution was precipitated in deionized water. The proposed fabrication route allowed obtaining a water-based dispersion of PEDOT:PSS nanospheres with good optical properties. To determine the physical properties of the nanospheres, we followed a nanoscale approach, using atomic force microscopy. Our nanoscale mechanical and electrical investigations showed that the nanospheres retained good physical and conductivity properties, compared to the commercial product. Moreover, the local studies indicated that the reprecipitation process and the spherical shape lead to a different arrangement of the PSS and PEDOT phases.

Intra- vs Intermolecular Cross-Links in Poly(methyl methacrylate) Networks Containing Enamine Bonds.

The molecular dynamics of a copolymer composed of methyl methacrylate (MMA) and (2-acetoacetoxy)ethyl methacrylate (AEMA) monomers and the influence on it of intra- to intermolecular cross-links of AEMA units with ethylenediamine (EDA) was studied by combining dielectric relaxation experiments and thermal investigations. The dielectric spectra of the non-cross-linked copolymer show three dynamical processes: a slow relaxation (α) and a faster (ß), both dominated by the MMA dynamics, and an even faster secondary relaxation (γ) reflecting the AEMA dynamics. Already for low cross-linking densities, the γ process is very much affected and eventually disappears, increasing the cross-linking density. The secondary ß relaxation however was nearly unaffected by cross-linking. The effect of cross-linking on the α relaxation was very pronounced with an important increasing of the glass transition temperature T g. There was also an increase of the dynamic heterogeneity and the relaxation intensity when increasing the cross-linking density (up to the maximum explored, 9 mol % EDA). The quality of the average time scale and T g value have similarities in behavior for intra- and intermolecular cross-linking, but clear differences in the dynamic heterogeneities where observed. These differences can be interpreted in connection with the sparse internal structure of the collapsed single chains obtained by intramolecular cross-linking.

Gold nanoparticles endowed with low-temperature colloidal stability by cyclic polyethylene glycol in ethanol.

The colloidal stability of metal nanoparticles is tremendously dependent on the thermal behavior of polymer brushes. Neat polyethylene glycol (PEG) presents an unconventional upper critical solution temperature in ethanol, where phase segregation and crystallization coexist. This thermal behavior translated to a PEG brush has serious consequences on the colloidal stability in ethanol of gold nanoparticles (AuNPs) modified with PEG brushes upon cooling. We observed that AuNPs (13 nm diameter) stabilized with conventional linear PEG brushes (Mn = 6 and 11 kg mol-1) in ethanol suffer from reversible phase separation upon a temperature drop over the course of a few hours. However, the use of a polymer brush with cyclic topology as a stabilizer prevents sedimentation, ensuring the colloidal stability in ethanol at -25 °C for, at least, four months. We postulate that temperature-driven collapse of chain brushes promotes the interpenetration of linear chains, causing progressive AuNP sedimentation, a process that is unfavorable for cyclic polymer brushes whose topology prevents chain interpenetration. This study reinforces the notion about the importance of polymer topology on the colloidal stability of AuNPs.

Phase Transitions in Poly(vinylidene fluoride)/Polymethylene-Based Diblock Copolymers and Blends.

The crystallization and morphology of two linear diblock copolymers based on polymethylene (PM) and poly(vinylidene fluoride) (PVDF) with compositions PM23-b-PVDF77 and PM38-b-PVDF62 (where the subscripts indicate the relative compositions in wt%) were compared with blends of neat components with identical compositions. The samples were studied by SAXS (Small Angle X-ray Scattering), WAXS (Wide Angle X-ray Scattering), PLOM (Polarized Light Optical Microscopy), TEM (Transmission Electron Microscopy), DSC (Differential Scanning Calorimetry), BDS (broadband dielectric spectroscopy), and FTIR (Fourier Transform Infrared Spectroscopy). The results showed that the blends are immiscible, while the diblock copolymers are miscible in the melt state (or very weakly segregated). The PVDF component crystallization was studied in detail. It was found that the polymorphic structure of PVDF was a strong function of its environment. The number of polymorphs and their amount depended on whether it was on its own as a homopolymer, as a block component in the diblock copolymers or as an immiscible phase in the blends. The cooling rate in non-isothermal crystallization or the crystallization temperature in isothermal tests also induced different polymorphic compositions in the PVDF crystals. As a result, we were able to produce samples with exclusive ferroelectric phases at specific preparation conditions, while others with mixtures of paraelectric and ferroelectric phases.

Water dynamics and self-assembly of single-chain nanoparticles in concentrated solutions.

Single-chain polymer nanoparticles (SCNPs) are soft nano-objects consisting of uni-macromolecular chains collapsed to a certain degree by intramolecular crosslinking. The similarities between the behaviour of SCNPs and that of intrinsically disordered proteins suggest that SCNPs in concentrated solutions can be used as models to design artificial micro-environments, which mimic many of the general aspects of cellular environments. In this work, the self-assembly into SCNPs of an amphiphilic random copolymer, composed by oligo(ethylene glycol)methyl ether methacrylate (OEGMA) and 2-acetoacetoxy ethyl methacrylate (AEMA), has been investigated by means of the dielectric relaxation of water. Direct evidence of segregation of the AEMA repeating units is provided by comparison with the dielectric relaxation of water in similar solutions of the linear hydrophilic polymer, P(OEGMA). Furthermore, the results of comparative studies with similar water solutions of an amphiphilic block copolymer forming multi-chain micelles support the single-chain character of the self-assembly of the random copolymer. The overall obtained results highlight the suitability of the dielectric spectroscopy to confirm the self-assembly of the amphiphilic random copolymers into globular like core-shell single-chain nanoparticles at a concentration well above the overlap concentration.

Effect of Paclitaxel in the Water Dynamics of MCF-7 Breast Cancer Cells Revealed by Dielectric Spectroscopy.

Using dielectric spectroscopy experiments performed at multiple temperatures and frequency ranges, we demonstrate how the chemotherapy drug paclitaxel changes the dynamic properties of water in a breast cancer cell line (MCF-7). From the measured data, we present evidence that treatment with paclitaxel leads to a slight increase in activation energy in a relaxation related to bulk-like water. More importantly, we also observe that paclitaxel changes the constraining imposed by the biological interfaces on hydration water, whose single-particle dynamics becomes slower and with higher activation energy. These variations are only observable after freezing the dynamics from other cellular components, such as proteins and DNAs, regardless of the state of the cells, that is, treated or not treated or even if the cells are no longer viable. Therefore, changes in water dynamics could be detected prior to those related to the global dynamics within the cellular environment.

Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s' Molecular Dynamics.

Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure-property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.

Effect of environmental humidity on the ionic transport of poly(ethylene oxide) thin films, investigated by local dielectric spectroscopy.

The effect of humidity on the ionic transport in the amorphous phase of poly(ethylene oxide) thin films has been studied by local dielectric spectroscopy. We explored a controlled humidity range between 15% RH and 50% RH. AFM-based local dielectric imaging allowed the thin film topography and the corresponding dielectric contrast maps to be obtained simultaneously. No humidity effect on the film topography was observed whereas large variation of the dielectric signal could be detected. In addition, we observed a clear dielectric contrast in different locations on the thin film surface. At selected regions with high contrast in the dielectric maps, we performed nanoDielectric Spectroscopy (nDS) measurements covering the frequency range from 5 Hz to 100 kHz. By modeling these spectroscopy results, we quantified the conductivity of the amorphous phase of the semicrystalline poly(ethylene oxide) films. The crystalline fraction of the PEO thin films was extracted and found to be about 36%, independently of humidity. However, the average conductivity increased by a factor of 25 from 2 × 10-10 to 5 × 10-9 S cm-1, by changing environmental humidity in the explored % RH range.

Dynamics of Confined Short-Chain alkanol in MCM-41 by Dielectric Spectroscopy: Effects of matrix and system Treatments and Filling Factor.

The dynamics of n-propanol confined in regular MCM-41 matrix with the pore size Dpore = 40 Å, under various matrix conditioning and sample confining conditions, using broadband dielectric spectroscopy (BDS), is reported. First, various drying procedures with the capacitor filling under air or N2 influence the BDS spectra of the empty MCM-41 and the confined n-PrOH/MCM-41 systems, but have a little effect on the maximum relaxation time of the main process. Finally, various filling factors of n-PrOH medium in the optimally treated MCM-41 system lead to unimodal or bimodal spectra interpreted in terms of the two distinct dynamic phases in the confined states.

Molecular Diversity of ESBL-Producing Escherichia coli from Foods of Animal Origin and Human Patients.

Dissemination of enterobacteria that produce extended spectrum ß-lactamases (ESBL) throughout the food chain has become an important health concern. This work aimed to evaluate the occurrence of ESBL-producing bacteria in foods of animal origin and to investigate the similarities between food and human isolates. The presence of beta-lactam-resistant Enterobacteriaceae was analyzed in 108 food samples, isolating 10 strains of Escherichia coli, one strain of Citrobacter freundi, and one of Hafnia alvei. E. coli isolates were compared to a group of 15 strains isolated from human patients by antibiotic susceptibility testing, characterization of ESBL genes (blaTEM, blaCTX,), multilocus sequence typing (MLST) and pulse-field gel electrophoresis (PFGE). Nineteen (14 clinical and five food) isolates carried blaCTX, 14 (six clinical and eight food) carried blaTEM, and three (one clinical and two food) carried blaSHV gen. MLST analysis revealed the prevalence of ST131 among the clinical strains, which grouped together in a PFGE cluster. Food isolates showed higher diversity and two of them (ST57) grouped with clinical strains, whereas another two belonged to clonal groups with virulence potential (ST59). In conclusion, the results showed that foods of animal origin must be regarded as a reservoir of ESBL-producing bacteria of clinical relevance, which might spread through the food chain.

Resolving Segmental Polymer Dynamics in Nanocomposites by Incoherent Neutron Spin-Echo Spectroscopy.

The segmental dynamics of styrene-butadiene nanocomposites with embedded silica nanoparticles (NPs, ca. 20 vol. %) has been studied by broadband dielectric (BDS) and neutron spin-echo spectroscopy (NSE). It is shown by BDS that overlapping contributions only allow us to conclude on a range of distributions of relaxation times in simplified industrial nanocomposites formed with highly polydisperse NPs. For comparison, structurally similar but less aggregated colloidal nanocomposites have a well-defined distribution of relaxation times due to the reduced influence of interfacial polarization processes. This distribution is widened with respect to the neat polymer, without change in the position of the maximum and at most a small slowing down visible in the average time. We then demonstrate that incoherent NSE can be used to resolve small modifications of segmental dynamics of the industrial samples. By carefully choosing the q-vector of the measurement, experiments with fully hydrogenated polymer give access to the self-dynamics of the polymer in the presence of silica on the scale of approximately 1 nm. Our high-resolution measurements show that the segmental motion is slightly but systematically slowed also by the presence of the industrial filler NPs.

Direct Observation of Dynamic Tube Dilation in Entangled Polymer Blends: A Combination of Neutron Scattering and Dielectric Techniques.

We report a microscopic observation of the time-dependent dynamic tube dilation process on isofrictional bidisperse melts. By applying neutron spin echo (NSE) and dielectric techniques on blends of long polyisoprene (PI) chains with short PI additives with different topology, we access the dynamics of the tube dilation process on a molecular scale. The time-dependent tube dilation is directly revealed by NSE as an additional time dependence of the dynamic structure factor in the local reptation regime. We identify the characteristic time of tube dilation as the terminal time of the additive.

How Confinement Affects the Nucleation, Crystallization, and Dielectric Relaxation of Poly(butylene succinate) and Poly(butylene adipate) Infiltrated within Nanoporous Alumina Templates.

This work describes the successful melt infiltration of poly(butylene succinate) (PBS) and poly(butylene adipate) (PBA) within 70 nm diameter anodic aluminum oxide (AAO) templates. The infiltrated samples were characterized by SEM, Raman, and FTIR spectroscopy. The crystallization behaviors and crystalline structures of both polymers, bulk and confined, were analyzed by differential scanning calorimetry (DSC) and grazing incidence wide angle X-ray scattering (GIWAXS). DSC revealed that a change in the nucleation process occurred from heterogeneous nucleation for bulk samples to homogeneous nucleation for infiltrated PBA and to surface-induced nucleation for infiltrated PBS. GIWAXS results indicate that PBS nanofibers crystallize in the α-phase, as well as their bulk samples. However, PBA nanofibers crystallize just in the ß-phase, whereas PBA bulk samples crystallize in a mixture of α- and ß-phases. The crystal orientation within the pores was determined, and differences between PBS and PBA were also found. Finally, broadband dielectric spectroscopy was applied to study the segmental dynamics for bulk and infiltrated samples. The glass temperature was found to significantly decrease in the PBS case upon infiltration, while that of PBA remained unchanged. These differences were correlated with the higher affinity of PBS to the AAO walls than PBA, in accordance with their nucleation behavior (surface-induced versus homogeneous nucleation, respectively).