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Copolymers based on vinylidene fluoride are potential materials for ferroelectric memory elements. The trend in studies showing that a decrease in the degree of crystallinity can lead to an unexpected increase in the electric breakdown field is noted. An analysis of the literature data reveals that in fluorine-containing ferroelectric polymers, when using a bipolar triangular field, the hysteresis loop has an unclosed shape, with each subsequent loop being accompanied by a decrease in the dielectric response. In this work, the effect of the structure of self-polarized films of copolymers of vinylidene fluoride with tetrafluoroethylene and hexafluoropropylene on breakdown processes was studied. The structure of the polymer films was monitored using infrared spectroscopy (IR) and X-ray diffraction. Kelvin probe force microscopy (KPFM) was applied to characterize the local electrical properties of the polymers. For the films of the first copolymer, which crystallize in the polar β-phase, asymmetry in the dielectric response was observed at fields greater than the coercive field. For the films of the copolymers of vinylidene fluoride with hexafluoropropylene, which crystallize predominantly in the nonpolar α-phase, polarization switching processes have also been observed, but at lower electric fields. The noted phenomena will help to identify the influence of the structure of ferroelectric polymers on their electrical properties. [ABSTRACT FROM AUTHOR]

In this work, a number of new porphyrin dimers coupled with spacers based on α,α'-dibromo-o-xylene were synthesized and characterized by 1H, 13C NMR, 1H-1H COSY NMR, UV-vis-spectroscopy, and MALDI-TOF mass spectrometry. The initial A3B-type hydroxy-substituted porphyrins form dimer structures with high yields of 80–85%, while the use of amino-substituted porphyrins as starting compounds leads to the heterocyclization and formation of N-heterocycle fused porphyrins. For porphyrin dimers, photophysical properties and quantum yields of singlet oxygen were investigated. The peripheral alkoxy-substituents increase fluorescence quantum yield in comparison with the unsubstituted compounds. Also, it was found that dimers are characterized by lower singlet oxygen quantum yields compared to the corresponding monomers. Model aggregation experiments in micellar systems demonstrate stabilization of the photoactive monomolecular form of all the porphyrins, using nonionic surfactant Triton X-100. Cytotoxicity of received dimers shows high inhibition against HEK293T cells in the absence of light. [ABSTRACT FROM AUTHOR]

The main reserve polysaccharide of plants—starch—is undoubtedly important for humans. One of the main sources of starch is the potato tuber, which is able to preserve starch for a long time during the so-called dormancy period. However, accumulated data show that this dormancy is only relative, which raises the question of the possibility of some kind of starch restructuring during dormancy periods. Here, the effect of long-term periods of tuber rest (at 2–4 °C) on main parameters of starches of potato tubers grown in vivo or in vitro were studied. Along with non-transgenic potatoes, Arabidopsis phytochrome B (AtPHYB) transformants were investigated. Distinct changes in starch micro and macro structures—an increase in proportion of amorphous lamellae and of large-sized and irregular-shaped granules, as well as shifts in thickness of the crystalline lamellae—were detected. The degree of such alterations, more pronounced in AtPHYB-transgenic tubers, increased with the longevity of tuber dormancy. By contrast, the polymorphic crystalline structure (B-type) of starch remained unchanged regardless of dormancy duration. Collectively, our data support the hypothesis that potato starch remains metabolically and structurally labile during the entire tuber life including the dormancy period. The revealed starch remodeling may be considered a process of tuber preadaptation to the upcoming sprouting stage. [ABSTRACT FROM AUTHOR]

Polymer films doped by different porphyrins, obtained by crystallization from the acetone solutions, differ in absorption and fluorescence spectra, which we attribute to the differences in the structuring and composition of the rotational isomers in the polymer chains. According to the infrared spectroscopy data, the crystallization of the films doped with tetraphenylporphyrin (TPP) proceeds in a mixture of α- and γ-phases with TGTG− and T3GT3G− conformations, respectively. Three bonds in the planar zigzag conformation ensures the contact of such segments with the active groups of the porphyrin macrocycle, significantly changing its electronic state. Structuring of the films in the presence of TPP leads to an increase in the low-voltage AC-conductivity and the registration of an intense Maxwell-Wagner polarization. An increased conductivity by an order of magnitude in TPP-doped films was also observed at high-voltage polarization. The introduction of TPP during the film formation promotes the displacement of the chemical attachment defects of "head-to-head" type in the monomeric units into the surface. This process is accompanied by a significant increase in the film surface roughness, which was registered by piezo-force microscopy. The latter method also revealed the appearance of hysteresis phenomena during the local piezoelectric coefficient d33 measurements. [ABSTRACT FROM AUTHOR]

A novel amphiphilic cationic chlorin e6 derivative was investigated as a promising photosensitizer for photodynamic therapy. Two cationic –N(CH3)3+ groups on the periphery of the macrocycle provide additional hydrophilization of the molecule and ensure its electrostatic binding to the mitochondrial membranes and bacterial cell walls. The presence of a hydrophobic phytol residue in the same molecule results in its increased affinity towards the phospholipid membranes while decreasing its stability towards aggregation in aqueous media. In organic media, this chlorin e6 derivative is characterized by a singlet oxygen quantum yield of 55%. Solubilization studies in different polymer- and surfactant-based supramolecular systems revealed the effective stabilization of this compound in a photoactive monomolecular form in micellar nonionic surfactant solutions, including Tween-80 and Cremophor EL. A novel cationic chlorin e6 derivative also demonstrates effective binding towards serum albumin, which enhances its bioavailability and promotes effective accumulation within the target tissues. Laser confocal scanning microscopy demonstrates the rapid intracellular accumulation and distribution of this compound throughout the cells. Together with low dark toxicity and a rather good photostability, this compound demonstrates significant phototoxicity against HeLa cells causing cellular damage most likely through reactive oxygen species generation. These results demonstrate a high potential of this derivative for application in photodynamic therapy. [ABSTRACT FROM AUTHOR]

This paper reports on the design and synthesis of new multifunctional porphyrin-based therapeutic agents for potential therapeutic and diagnostic applications. Zinc complexes of A3B-type meso-arylporphyrins containing OH- and COOH- groups were modified with chelating ligands based on 4′-(4-methylphenyl)-2,2′:6′,2″-terpyridine derivatives in high yields. Novel complexes with Gd(III), Fe(III) were obtained for these conjugates. Aggregation behaviour in solutions of different solubilisers was studied to inform the selection of the optimal solubilising platform for the porphyrins obtained; their photophysical and photochemical properties were also characterised. Micellar Pluronic F127 formulation was found to be the most effective solubiliser for stabilising the fluorescence-active monomolecular form of the photosensitisers (PS). In vitro cytotoxicity of the compounds was studied on the HEP-2 cell line with and without irradiation for 1.5 and 24 h. As a result, the IC50 of compounds 12 and 14 at an irradiation dose of 8.073 J/cm2 was shown to be 1.87 ± 0.333 and 1.4 ± 0.152 μM, respectively; without irradiation, the compound had no toxic effect within the studied concentration range (1.5 h). A test for the inhibition of metabolic cooperation or promoter activity was also performed for the abovementioned compounds, showing the efficacy and safety of the conjugates obtained. Preliminary data have indicated the high potential of the new type of PS to be promising molecular theranostic agents. [ABSTRACT FROM AUTHOR]

General problems of structural changes which occur at storage of two‐phase crystalline polymers with a metastable structure at room conditions are considered on the example of a vinylidene fluoride ‐ hexafluoropropylene copolymer. The physical aging occurs in flexible‐chain crystalline polymers (polyethylene, fluoropolymers under consideration, etc.), where, due to low glass transition temperatures, the liquid‐like dynamics of amorphous phase chains is realized at room temperature through cooperative micro‐Brownian motions with short relaxation times. Taking into account that covalent‐bound sections of the chains of the amorphous phase can enter the crystallites, the noted mobility may initiate changes in the size of the latter. Such a possibility is proved by the example of the noted copolymer. At low‐temperature crystallization of a vinylidene fluoride ‐ hexafluoropropylene copolymer from a solution the formed α‐phase crystals have little perfection. The size of the crystals increases when the films are stored in room conditions. Because of the crystal polymorphism, at the same time a certain fraction of γ‐phase crystals which are present in initial films undergo a polymorphic transformation γ → α. These processes lead to an increase in crystallinity. Moreover, during such processes additional structuring is observed, which is reduced to the displacement of various kinds of intra‐chain defects into the amorphous phase (and especially into the surface). Since the copolymers under study are ferroelectrics, they were studied by piezo force microscopy. It was found that despite the crystallization predominantly in nonpolar α‐phase, piezo force microscopy revealed a domain structure, which formation mechanism is discussed. The structural changes at physical aging of the films affect the character of the noted domain structure. Thus, it is suggested that the mechanism of the described structural changes is realized through the developed cooperative mobility of the chains in the amorphous phase, which characterizes the processes of rotational diffusion. [ABSTRACT FROM AUTHOR]

The purpose of this work is to study the dielectric charging of polymer fibers with the electron plasma charging effects accompanied by the emergence of waves propagating along the polymer fiber surface. Monitoring of the charge propagation along the single fiber has been performed using dielectric polyhydroxybutyrate (PHB) fibers obtained by the electrospinning (ESP) method under the electron beam inside the scanning electron microscope chamber. The mechanical effect of the electron beam on the polymer fibers has been detected in a time-lapse mode. The influence of the polymer surface irregularities and mechanical defects on the fiber charging has been demonstrated. Plasma mechanism is typical not only for electrophysical phenomena but also for the control of mechanical movement of the fibers by the electron beam and the charge propagation during electron-beam-induced melting and in the presence of hydrodynamic polymer flows. It is assumed that the mechanical effect in the methods using an electron beam (and plasma on the dielectric surface) as an impact source can be determined by the following factors: pressure of the electron beam and the electric field, contribution of the secondary emission, thermal/thermomechanical factors, and dynamic balance or competition between all the forces affecting the sample (electron-beam pressure, gravity pressure, recoil pressure during evaporation, vapor pressure/surface tension, and so on). In addition to purely scientific interest, the above phenomena are also of significant applied interest since the influence of the polymer fiber charging on the separation procedure of aerosols in nonwoven filters is well known, and hence, charging of such polymer fibers is important for some energy storage devices. [ABSTRACT FROM AUTHOR]

A unique chemical analytical approach is proposed based on the integration of chemical radiophysics with electrochemistry at the catalytically-active surface. This approach includes integration of: radiofrequency modulation polarography with platinum electrodes, applied as film enthrakometers for microwave measurements; microwave thermal analysis performed on enthrakometers as bolometric sensors; catalytic measurements, including registration of chemical self-oscillations on the surface of a platinum enthrakometer as the chemosensor; measurements on the Pt chemosensor implemented as an electrochemical chip with the enthrakometer walls acting as the chip walls; chemotron measurements and data processing in real time on the surface of the enthrakometric chip; microwave electron paramagnetic resonance (EPR) measurements using an enthrakometer both as a substrate and a microwave power meter; microwave acceleration of chemical reactions and microwave catalysis оn the Pt surface; chemical generation of radio- and microwaves, and microwave spin catalysis; and magnetic isotope measurements on the enthrakometric chip. The above approach allows one to perform multiparametric physical and electrochemical sensing on a single active enthrakometric surface, combining the properties of the selective electrochemical sensor and an additive physical detector. [ABSTRACT FROM AUTHOR]