Direct and indirect effects on molecular mobility in renewable polylactide-poly(propylene adipate) block copolymers as studied via dielectric spectroscopy and calorimetry.

In this work, we study a series of sustainable block copolymers based on polylactide, PLA, and poly(propylene adipate), PPAd, both polymers being prepared from renewable resources. Envisaging a wide range of future applications in the frame of a green and circular economy, e.g., packaging materials replacing conventional petrochemicals, the employment of PPAd aims at lowering the glass transition and melting temperatures of PLA and, finally, facilitation of the enzymatic degradation and compostability. The copolymers have been synthesized via ring opening polymerization of lactides in the presence of propylene adipate oligomers (5, 15 and 25%). The direct effects on the molecular mobility by the structure/composition are assessed in the amorphous state employing broadband dielectric spectroscopy (BDS) and calorimetry. BDS allowed the recording of local PLA and PPAd dynamics in all cases. The effects on local relaxations suggest favoring of interchain interactions, both PLA-PPAd and PPAd-PPAd. Regarding the more important segmental dynamics, the presence of PPAd leads to faster polymer chain diffusion, as monitored by the significant lowering of the dielectric and calorimetric glass transition temperature, Tg. This suggests the plasticizing role of PPAd on PLA (majority) in combination with the lowering of the average molar mass, Mn, in the copolymers from ∼75 to ∼30 kg mol-1, which is the actual scope for the synthesis of these materials. Interestingly, a strong suppression in fragility (chain cooperativity) is additionally recorded. In contrast to calorimetry and due to the high resolving power of BDS, for the higher PPAd fraction, the weak segmental relaxation of PPAd was additionally recorded. Overall, the recordings suggest a strong increase in free volume and two individual dynamic states, one for 0 and 5% PPAd and another for 15 and 25% PPAd. Within the latter, we gained indications for partial phase nano-separation of PPAd. Regarding indirect effects, these were followed via crystallization. Independent of the method of crystallization, namely, melt or cold, the presence of PPAd led to the systematic lowering of crystallization and melting temperatures and enthalpies. The effects reflect the decrease of crystalline nuclei, which is confirmed by optical microscopy as in the copolymers fewer although larger crystals are formed.

Effects of CNTs on thermal transitions, thermal diffusivity and electrical conductivity in nanocomposites: comparison between an amorphous and a semicrystalline polymer matrix.

Two series of polymer nanocomposites (PNCs) based on amorphous styrene-butadiene rubber (SBR) and semicrystalline linear low-density polyethylene (PE) matrices were filled with 2-15 wt% carbon nanotubes (CNT) and were studied by employing calorimetry, dielectric spectroscopy and laser flash analysis. The electrical conductivity, σ, increased with CNT loading and similar values were exhibited for the two matrices, uniquely depending on the concentration of the CNTs, suggesting practically no effects of the crystalline fraction (CF) on σ. For both types of matrix, a fraction of the polymer was found to be immobilized (rigid amorphous fraction, RAF). For the amorphous SBR, the RAF in PNCs originates uniquely from the presence of the filler (RAFfiller up to 0.19 wt). On the other hand, for the semicrystalline PE, the RAF is significantly larger (0.4-0.6 wt) due to the severe contribution of the RAF around the crystals (RAFcrystal). The thermal diffusivity, α, is quite low in both types of PNCs and exhibits higher values in the semicrystalline matrix (PE-based PNCs). Our results suggest that in these PNCs, heat transport mechanisms are activated mainly in the crystalline domains, more so with the additive contribution of the RAFcrystal. In the amorphous SBR-based PNCs, heat transport is facilitated mainly by CNTs, whereas the RAFfiller is found to be a good measure of the thermal resistance behavior of CNT/polymer interphases and consequently, of thermal diffusivity. Direct correlation of the results obtained by the three techniques with each other revealed the systematic dependence of α on the amount of RAF in each matrix; the α(RAF) trends, however, are different for the two matrices. Furthermore, the results suggest that the two RAFs exhibit different structural characteristics, e.g. the RAFcrystal exhibits a more ordered structure than the RAFfiller; this issue is still an open debate in the literature.

Dynamic glass transition of the rigid amorphous fraction in polyurethane-urea/SiO2 nanocomposites.

We report molecular dynamics in the rigid amorphous fraction (RAF) of the polymer bound at the interfaces with nanoparticles in polymer nanocomposites and calculate the glass transition temperature, Tg, for this bound layer of polymer. We follow the '3-phase-model' for semicrystalline polymers where the polymer matrix consists of the crystalline fraction (CF), the mobile amorphous fraction (MAF) and the RAF. While the amorphous polymer bound by crystallites is completely rigid, neither contributing to the glass transition, nor displaying molecular dynamics, the amorphous polymer bound at the interfaces with filler displays decelerated dynamics, as compared to the bulk polymer. Reports in the literature suggest a discrepancy between Tg values obtained by Differential Scanning Calorimetry (DSC) and by Dielectric Relaxation Spectroscopy (DRS). As a plausible explanation we suggest that DRS results in Tg values taking into account the bound polymer, whereas DSC does not. For this investigation we use semicrystalline polyurethane-urea/SiO2 nanocomposites and employ, next to DSC and DRS, SEM, SAXS and WAXS for morphological characterization. It is our intention to use DRS as a tool for investigating the RAF.

Applying Broadband Dielectric Spectroscopy (BDS) for the Biophysical Characterization of Mammalian Tissues under a Variety of Cellular Stresses.

The dielectric properties of biological tissues can contribute non-invasively to a better characterization and understanding of the structural properties and physiology of living organisms. The question we asked, is whether these induced changes are effected by an endogenous or exogenous cellular stress, and can they be detected non-invasively in the form of a dielectric response, e.g., an AC conductivity switch in the broadband frequency spectrum. This study constitutes the first methodological approach for the detection of environmental stress-induced damage in mammalian tissues by the means of broadband dielectric spectroscopy (BDS) at the frequencies of 1-106 Hz. Firstly, we used non-ionizing (NIR) and ionizing radiation (IR) as a typical environmental stress. Specifically, rats were exposed to either digital enhanced cordless telecommunication (DECT) radio frequency electromagnetic radiation or to γ-radiation, respectively. The other type of stress, characterized usually by high genomic instability, was the pathophysiological state of human cancer (lung and prostate). Analyzing the results of isothermal dielectric measurements provided information on the tissues' water fraction. In most cases, our methodology proved sufficient in detecting structural changes, especially in the case of IR and malignancy. Useful specific dielectric response patterns are detected and correlated with each type of stress. Our results point towards the development of a dielectric-based methodology for better understanding and, in a relatively invasive way, the biological and structural changes effected by radiation and developing lung or prostate cancer often associated with genomic instability.

Role of oxidative stress and DNA damage in human carcinogenesis.

Cells in tissues and organs are continuously subjected to oxidative stress and free radicals on a daily basis. This free radical attack has exogenous or endogenous (intracellular) origin. The cells withstand and counteract this occurrence by the use of several and different defense mechanisms ranging from free radical scavengers like glutathione (GSH), vitamins C and E and antioxidant enzymes like catalase, superoxide dismutase and various peroxidases to sophisticated and elaborate DNA repair mechanisms. The outcome of this dynamic equilibrium is usually the induction of oxidatively induced DNA damage and a variety of lesions of small to high importance and dangerous for the cell i.e. isolated base lesions or single strand breaks (SSBs) to complex lesions like double strand breaks (DSBs) and other non-DSB oxidatively generated clustered DNA lesions (OCDLs). The accumulation of DNA damage through misrepair or incomplete repair may lead to mutagenesis and consequently transformation particularly if combined with a deficient apoptotic pathway. In this review, we present the current status of knowledge and evidence on the mechanisms and involvement of intracellular oxidative stress and DNA damage in human malignancy evolution and possible use of these parameters as cancer biomarkers. At the same time, we discuss controversies related to potential artifacts inherent to specific methodologies used for the measurement of oxidatively induced DNA lesions in human cells or tissues.

Dynamics of Uncrystallized Water, Ice, and Hydrated Protein in Partially Crystallized Gelatin-Water Mixtures Studied by Broadband Dielectric Spectroscopy.

The glass transition of partially crystallized gelatin-water mixtures was investigated using broadband dielectric spectroscopy (BDS) over a wide range of frequencies (10 mHz to 10 MHz), temperatures (113-298 K), and concentrations (10-45 wt %). Three dielectric relaxation processes (processes I, II, and III) were clearly observed. Processes I, II, and III originate from uncrystallized water (UCW) in the hydration shells of gelatin, ice, and hydrated gelatin, respectively. A dynamic crossover, called the Arrhenius to non-Arrhenius transition of UCW, was observed at the glass transition temperature of the relaxation process of hydrated gelatin for all mixtures. The amount of UCW increases with increasing gelatin content. However, above 35 wt % gelatin, the amount of UCW became more dependent on the gelatin concentration. This increase in UCW causes a decrease in the glass transition temperature of the cooperative motion of gelatin and UCW, which appears to result from a change in the aggregation structure of gelatin in the mixture at a gelatin concentration of approximately 35 wt %. The temperature dependence of the relaxation time of process II has nearly the same activation energy as pure ice made by slow crystallization of ice Ih. This implies that process II originates from the dynamics of slowly crystallized ice Ih.

Effects of Solvent Crystallization in Swollen net-Poly(ethyl acrylate) α Relaxation Dynamics.

The polymer α relaxation process for net-PEA gels swollen with nonpolar p-xylene is studied by employing dielectric relaxation spectroscopy. The results present the in situ monitoring of the dielectric behavior of α relaxation process under p-xylene cold crystallization, isothermal crystallization as well as crystallization from quenching. For the partially crystallized systems, the results exhibit that the amount of p-xylene crystal phase has no remarkable effects on the time scale, being controlled mainly by the amount of the noncrystallized p-xylene (cpx= 0.11-0.15) gel phase. Surprisingly, the stretching exponent ßKWW obtains higher values in the isothermal crystallization process as the p-xylene crystallization is in progress and the reorganization of p-xylene through diffusion to crystallites approaches thermodynamic equilibrium. This directly indicates that any α process broadening is originated not solely from the amount of p-xylene crystallites and the induced heterogeneities, but from the presence of remarkable concentration fluctuations close to respective effective glass transition temperature, enhanced for higher solvent contents as well. Finally, the results suggest that the existence of p-xylene crystallites decrease significantly the dielectric strength of α process. The effective medium theory is applied to check whether this recorded reduction originates from the induced spatial heterogeneities (p-xylene crystallites) or from the immobilization in parts of polymer configurations.

Phase transitions in crystals of racemic long chain 2-amino alcohols.

Various techniques, namely differential scanning calorimetry, optical microscopy, dielectric and Raman spectroscopy, all covering a wide range of temperatures, were used to study the thermodynamically stable phases and molecular mobility of crystals of long chain 2-amino alcohols. The results showed that two different crystal forms are present in each sample. The temperature behaviour of the phases is studied in details.

Phase behaviour of transkarbam 12.

Transkarbam 12 (T12), the carbamic acid salt of omega-aminocaproic acid dodecyl ester, is a recently synthesized substance, whose high permeation enhancing activity through the human skin was found for certain drugs. In this work, the thermotropic phase behaviour of T12 has been studied by means of various techniques, namely, DSC, FTIR and FT-Raman spectroscopy, X-ray powder diffraction, and DRS. The temperature development of the X-ray reflections as well as of the conformationally sensitive Raman bands and the IR bands have been observed. At room temperature, the hydrocarbon chains of T12 exhibit a highly ordered structure, arranged in an orthorhombic perpendicular subcell. On heating, two transitions occur at 54 and at 66 degrees C. The first transition is related to the disruption of the carbamate structure and changes in the polar head group. The other transition represents the melting of hydrocarbon chains and the subsequent release of carbon dioxide. The time required for the rebinding of carbon dioxide and the reformation of the carbamate structure is dependent upon numerous factors and it was not possible to precisely determine the length of this process.

Relaxation processes at the glass transition in polyamide 11: from rigidity to viscoelasticity.

Relaxation processes associated with the glass transition in nonferroelectric and ferroelectric polyamide (PA) 11 are investigated by means of differential scanning calorimetry, dynamic mechanical analysis, and dielectric relaxation spectroscopy (DRS) in order to obtain information about the molecular mobility within the amorphous phase. In particular, the effects of melt quenching, cold drawing, and annealing just below the melting region are studied with respect to potential possibilities and limitations for improving the piezoelectric and pyroelectric properties of PA 11. A relaxation map is obtained from DRS that shows especially the crossover region where the cooperative alpha relaxation and the local beta relaxation merge into a single high-temperature process. No fundamental difference between quenched, cold-drawn, and annealed films is found, though in the cold-drawn (ferroelectric) film the alpha relaxation is suppressed and slowed down, but it is at least partly recovered by subsequent annealing. It is concluded that there exists an amorphous phase in all structures, even in the cold-drawn film. The amorphous phase can be more rigid or more viscoelastic depending on preparation. Cold drawing not only leads to crystallization in a ferroelectric form but also to higher rigidity of the remaining amorphous phase. Annealing just below the melting region after cold drawing causes a stronger phase separation between the crystalline phase and a more viscoelastic amorphous phase.