The Effect of the Thermosensitive Biodegradable PLGA⁻PEG⁻PLGA Copolymer on the Rheological, Structural and Mechanical Properties of Thixotropic Self-Hardening Tricalcium Phosphate Cement.

The current limitations of calcium phosphate cements (CPCs) used in the field of bone regeneration consist of their brittleness, low injectability, disintegration in body fluids and low biodegradability. Moreover, no method is currently available to measure the setting time of CPCs in correlation with the evolution of the setting reaction. The study proposes that it is possible to improve and tune the properties of CPCs via the addition of a thermosensitive, biodegradable, thixotropic copolymer based on poly(lactic acid), poly(glycolic acid) and poly(ethylene glycol) (PLGA⁻PEG⁻PLGA) which undergoes gelation under physiological conditions. The setting times of alpha-tricalcium phosphate (α-TCP) mixed with aqueous solutions of PLGA⁻PEG⁻PLGA determined by means of time-sweep curves revealed a lag phase during the dissolution of the α-TCP particles. The magnitude of the storage modulus at lag phase depends on the liquid to powder ratio, the copolymer concentration and temperature. A sharp increase in the storage modulus was observed at the time of the precipitation of calcium deficient hydroxyapatite (CDHA) crystals, representing the loss of paste workability. The PLGA⁻PEG⁻PLGA copolymer demonstrates the desired pseudoplastic rheological behaviour with a small decrease in shear stress and the rapid recovery of the viscous state once the shear is removed, thus preventing CPC phase separation and providing good cohesion. Preliminary cytocompatibility tests performed on human mesenchymal stem cells proved the suitability of the novel copolymer/α-TCP for the purposes of mini-invasive surgery.

Study of the Synthesis of Multi-Cationic Sm-Co-O, Sm-Ni-O, Al-Co-O, Al-Ni-O, and Al-Co-Ni-O Aerogels and Their Catalytic Activity in the Dry Reforming of Methane.

Dense multi-cationic Sm-Co-O, Sm-Ni-O, Al-Co-O, Al-Ni-O, and Al-Ni-Co-O oxide aerogels were prepared by epoxide-driven sol-gel synthesis. Catalysts for dry reformation of methane, Sm2O3/Co, Sm2O3/Ni, Al2O3/Co, Al2O3/Ni, Al2O3/Co, and Ni were prepared by reduction of aerogels with hydrogen and their catalytic activities and C-deposition during dry reformation of methane were tested. Catalytic tests showed high methane conversion (93-98%) and C-deposition (0.01-4.35 mg C/gcat.h). The highest content of C-deposits after catalytic tests was determined for Al2O3/Co and Al2O3/Ni catalysts, which was related to the formation of Al alloys with Co and Ni. A uniform distribution of Co0 and Ni0 nanoparticles (in the form of a CoNi alloy) was found only for the Al2O3/Co and Ni catalysts, which showed the highest activity as well as low C deposition.

Preserving Metamagnetism in Self-Assembled FeRh Nanomagnets.

Preparing and exploiting phase-change materials in the nanoscale form is an ongoing challenge for advanced material research. A common lasting obstacle is preserving the desired functionality present in the bulk form. Here, we present self-assembly routes of metamagnetic FeRh nanoislands with tunable sizes and shapes. While the phase transition between antiferromagnetic and ferromagnetic orders is largely suppressed in nanoislands formed on oxide substrates via thermodynamic nucleation, we find that nanomagnet arrays formed through solid-state dewetting keep their metamagnetic character. This behavior is strongly dependent on the resulting crystal faceting of the nanoislands, which is characteristic of each assembly route. Comparing the calculated surface energies for each magnetic phase of the nanoislands reveals that metamagnetism can be suppressed or allowed by specific geometrical configurations of the facets. Furthermore, we find that spatial confinement leads to very pronounced supercooling and the absence of phase separation in the nanoislands. Finally, the supported nanomagnets are chemically etched away from the substrates to inspect the phase transition properties of self-standing nanoparticles. We demonstrate that solid-state dewetting is a feasible and scalable way to obtain supported and free-standing FeRh nanomagnets with preserved metamagnetism.

Piezo-Enhanced Photocatalytic Activity of the Electrospun Fibrous Magnetic PVDF/BiFeO3 Membrane.

Creating stimulus-sensitive smart catalysts capable of decomposing organic dyes with high efficiency is a critical task in ecology. Combining the advantages of photoactive piezoelectric nanomaterials and ferroelectric polymers can effectively solve this problem by collecting mechanical vibrations and light energy. Using the electrospinning method, we synthesized hybrid polymer-inorganic nanocomposite fiber membranes based on polyvinylidene fluoride (PVDF) and bismuth ferrite (BFO). The samples were studied by scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), total transmittance and diffuse reflectance, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), vibrating-sample magnetometer (VSM), and piezopotential measurements. It has been demonstrated that the addition of BFO leads to an increase in the proportion of the polar phase from 86.5% to 96.1% due to the surface ion-dipole interaction. It is shown that the composite exhibits anisotropy of magnetic properties depending on the orientation of the magnetic field. The results of piezo-photocatalytic experiments showed that under the combined action of ultrasonic treatment and irradiation with both visible and UV light, the reaction rate increased in comparison with photolysis, sonolysis, and piezocatalysis. Moreover, for PVDF/BFO, which does not exhibit photocatalytic activity, under the combined action of light and ultrasound, the reaction rate increases by about 3× under UV irradiation and by about 6× under visible light irradiation. This behavior is explained by the piezoelectric potential and the narrowing of the band gap of the composite due to mechanical stress caused by the ultrasound.

Triboelectric Response of Electrospun Stratified PVDF and PA Structures.

Utilizing the triboelectric effect of the fibrous structure, a very low cost and straightforward sensor or an energy harvester can be obtained. A device of this kind can be flexible and, moreover, it can exhibit a better output performance than a device based on the piezoelectric effect. This study is concerned with comparing the properties of triboelectric devices prepared from polyvinylidene fluoride (PVDF) fibers, polyamide 6 (PA) fibers, and fibrous structures consisting of a combination of these two materials. Four types of fibrous structures were prepared, and then their potential for use in triboelectric devices was tested. Namely, individual fibrous mats of (i) PVDF and (ii) PA fibers, and their combination-(iii) PVDF and PA fibers intertwined together. Finally, the fourth kind was (iv), a stratified three-layer structure, where the middle layer from PVDF and PA intertwined fibers was covered by PVDF fibrous layer on one side and by PA fibrous layer on the opposite side. Dielectric properties were examined and the triboelectric response was investigated in a simple triboelectric nanogenerator (TENG) of individual or combined (i-iv) fibrous structures. The highest triboelectric output voltage was observed for the stratified three-layer structure (the structure of iv type) consisting of PVDF and PA individual and intertwined fibrous layers. This TENG generated 3.5 V at peak of amplitude at 6 Hz of excitation frequency and was most sensitive at the excitation signal. The second highest triboelectric response was observed for the individual PVDF fibrous mat, generating 2.8 V at peak at the same excitation frequency. The uniqueness of this work lies in the dielectric and triboelectric evaluation of the fibrous structures, where the materials PA and PVDF were electrospun simultaneously with two needles and thus created a fibrous composite. The structures showed a more effective triboelectric response compared to the fibrous structure electrospun by one needle.

Electrode Spacing as a Determinant of the Output Performance of Planar-Type Photodetectors Based on Methylammonium Lead Bromide Perovskite Single Crystals.

Methylammonium lead bromide is a very perspective hybrid semiconductor material, suitable for high-sensitive, filter-free photodetection of electromagnetic radiation. Herein, we studied the effect of electrode spacing on the output performance and stability of planar-type photodetectors based on high-quality MAPbBr3 single crystals. Such crystals, as large as 4.5×4.5×1.2 mm3 were synthesized via the inverse temperature crystallization method and were further used for the fabrication of planar Au/MAPbBr3/Au photodetectors with variable electrode spacing (in the range between 125 and 25 µm). We report that the electrode spacing has a profound impact on photocurrent densities and key detector parameters (responsivity R, external quantum efficiency EQE, and specific detectivity D*). In the studied fivefold electrode spacing, the photocurrent density increased over 4 times, with decreasing active area of the devices. This effect is attributed to intrinsic photocurrent amplification. Based on the transient photocurrent measurements and calculated key parameters, we determined the device sample with the best output performance. The champion sample with an electrode spacing of 50 µm exhibited great detection ability, especially for a low light intensity of 200 nWcm-2, for which we calculated the R of 19.55 A W-1, EQE of 4253%, and D* of 3.42 × 1012 Jones (cm Hz1/2 W-1). Moreover, the functional stability of this device showed a minimal reduction of photodetection ability after 2000 cycles, which makes it very promising for the next generation of optoelectronic devices.

Comprehensive Characterization of PVDF Nanofibers at Macro- and Nanolevel.

This study is focused on the characterization and investigation of polyvinylidene fluoride (PVDF) nanofibers from the point of view of macro- and nanometer level. The fibers were produced using electrostatic spinning process in air. Two types of fibers were produced since the collector speed (300 rpm and 2000 rpm) differed as the only one processing parameter. Differences in fiber's properties were studied by scanning electron microscopy (SEM) with cross-sections observation utilizing focused ion beam (FIB). The phase composition was determined by Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy. The crystallinity was determined by differential scanning calorimetry (DSC), and chemical analysis of fiber's surfaces and bonding states were studied using X-ray photoelectron spectroscopy (XPS). Other methods, such as atomic force microscopy (AFM) and piezoelectric force microscopy (PFM), were employed to describe morphology and piezoelectric response of single fiber, respectively. Moreover, the wetting behavior (hydrophobicity or hydrophilicity) was also studied. It was found that collector speed significantly affects fibers alignment and wettability (directionally ordered fibers produced at 2000 rpm almost super-hydrophobic in comparison with disordered fibers spun at 300 rpm with hydrophilic behavior) as properties at macrolevel. However, it was confirmed that these differences at the macrolevel are closely connected and originate from nanolevel attributes. The study of single individual fibers revealed some protrusions on the fiber's surface, and fibers spun at 300 rpm had a core-shell design, while fibers spun at 2000 rpm were hollow.

Structure Tuning and Electrical Properties of Mixed PVDF and Nylon Nanofibers.

The paper specifies the electrostatic spinning process of specific polymeric materials, such as polyvinylidene fluoride (PVDF), polyamide-6 (PA6, Nylon-6) and their combination PVDF/PA6. By combining nanofibers from two different materials during the spinning process, new structures with different mechanical, chemical, and physical properties can be created. The materials and their combinations were subjected to several measurements: scanning electron microscopy (SEM) to capture topography; contact angle of the liquid wettability on the sample surface to observe hydrophobicity and hydrophilicity; crystallization events were determined by differential scanning calorimetry (DSC); X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Fourier-transform infrared spectroscopy (FT-IR) to describe properties and their changes at the chemical level. Furthermore, for the electrical properties of the sample, the dielectric characteristics and the piezoelectric coefficient were measured. The advantage of the addition of co-polymers was to control the properties of PVDF samples and understand the reasons for the changed functionality. The innovation point of this work is the complex analysis of PVDF modification caused by mixing with nylon PA6. Here we emphasize that the application of nylon during the spin influences the properties and structure (polarization, crystallization) of PVDF.

Case Study of Polyvinylidene Fluoride Doping by Carbon Nanotubes.

Modern material science often makes use of polyvinylidene fluoride thin films because of various properties, like a high thermal and chemical stability, or a ferroelectric, pyroelectric and piezoelectric activity. Fibers of this polymer material are, on the other hand, much less explored due to various issues presented by the fibrous form. By introducing carbon nanotubes via electrospinning, it is possible to affect the chemical and electrical properties of the resulting composite. In the case of this paper, the focus was on the further improvement of interesting polyvinylidene fluoride properties by incorporating carbon nanotubes, such as changing the concentration of crystalline phases and the resulting increase of the dielectric constant and conductivity. These changes in properties have been explored by several methods that focused on a structural, chemical and electrical point of view. The resulting obtained data have been documented to create a basis for further research and to increase the overall understanding of the properties and usability of polyvinylidene fluoride fiber composites.

PVDF Fibers Modification by Nitrate Salts Doping.

The method of inclusion of various additives into a polymer depends highly on the material in question and the desired effect. In the case of this paper, nitride salts were introduced into polyvinylidene fluoride fibers prepared by electrospinning. The resulting changes in the structural, chemical and electrical properties of the samples were observed and compared using SEM-EDX, DSC, XPS, FTIR, Raman spectroscopy and electrical measurements. The observed results displayed a grouping of parameters by electronegativity and possibly the molecular mass of the additive salts. We virtually demonstrated elimination of the presence of the γ-phase by addition of Mg(NO3)2, Ca(NO3)2, and Zn(NO3)2 salts. The trend of electrical properties to follow the electronegativity of the nitrate salt cation is demonstrated. The performed measurements of nitrate salt inclusions into PVDF offer a new insight into effects of previously unstudied structures of PVDF composites, opening new potential possibilities of crystalline phase control of the composite and use in further research and component design.

Influence of Hydroxyapatite Nanoparticles and Surface Plasma Treatment on Bioactivity of Polycaprolactone Nanofibers.

Nanofibers are well known as a beneficial type of structure for tissue engineering. As a result of the high acquisition cost of the natural polymers and their environmentally problematic treatment (toxic dissolution agents), artificial polymers seem to be the better choice for medical use. In the present study, polycaprolactone nano-sized fibrous structures were prepared by the electrospinning method. The impact of material morphology (random or parallelly oriented fibers versus continuous layer) and the presence of a fraction of hydroxyapatite nanoparticles on cell proliferation was tested. In addition, the effect of improving the material wettability by a low temperature argon discharge plasma treatment was evaluated, too. We have shown that both hydroxyapatite particles as well as plasma surface treatment are beneficial for the cell proliferation. The significant impact of both influences was evident during the first 48 h of the test: the hydroxyapatite particles in polycaprolactone fibers accelerated the proliferation by 10% compared to the control, and the plasma-treated ones enhanced proliferation by 30%.

Structure-Properties Relationship of Electrospun PVDF Fibers.

Electrospinning as a versatile technique producing nanofibers was employed to study the influence of the processing parameters and chemical and physical parameters of solutions on poly(vinylidene fluoride) (PVDF) fibers' morphology, crystallinity, phase composition and dielectric and piezoelectric characteristics. PVDF fibrous layers with nano- and micro-sized fiber diameters were prepared by a controlled and reliable electrospinning process. The fibers with diameters from 276 nm to 1392 nm were spun at a voltage of 25 kV-50 kV from the pure PVDF solutions or in the presence of a surfactant-Hexadecyltrimethylammonium bromide (CTAB). Although the presence of the CTAB decreased the fibers' diameter and increased the electroactive phase content, the piezoelectric performance of the PVDF material was evidently deteriorated. The maximum piezoelectric activity was achieved in the fibrous PVDF material without the use of the surfactant, when a piezoelectric charge of 33 pC N-1 was measured in the transversal direction on a mean fiber diameter of 649 nm. In this direction, the material showed a higher piezoelectric activity than in the longitudinal direction.

Characterization of Polyvinylidene Fluoride (PVDF) Electrospun Fibers Doped by Carbon Flakes.

Polyvinylidene fluoride (PVDF) is a modern polymer material used in a wide variety of ways. Thanks to its excellent resistance to chemical or thermal degradation and low reactivity, it finds use in biology, chemistry, and electronics as well. By enriching the polymer with an easily accessible and cheap variant of graphite, it is possible to affect the ratio of crystalline phases. A correlation between the ratios of crystalline phases and different properties, like dielectric constant as well as piezo- and triboelectric properties, has been found, but the relationship between them is highly complex. These changes have been observed by a number of methods from structural, chemical and electrical points of view. Results of these methods have been documented to create a basis for further research and experimentation on the usability of this combined material in more complex structures and devices.

Prevalent anatase crystalline phase increases the cytotoxicity of biphasic titanium dioxide nanoparticles in mammalian cells.

Nanoparticular form of titanium dioxide (TiO2 NPs) belongs to important industrial material. Despite being widely used, serious contradictions regarding biosafety of TiO2 NPs remain. We anticipate that such discrepancies could be due to a lack of understanding of a linkage between TiO2 NPs phase composition and cytotoxicity. Therefore, we synthesized two types of biphasic TiO2 NPs differing in an anatase-brookite phase composition. The study presents an array of in vitro data suggesting that TiO2 NPs with a prevailing anatase phase composition possess higher cytotoxicity compared to TiO2 NPs with an equal anatase-brookite crystallinity. This phenomenon was evidenced by significantly higher inhibition of metabolic activity and growth of epithelial and neuroblast-like cells. Moreover, anatase-prevailing TiO2 NPs tend to produce higher amount of reactive oxygen species resulting in DNA fragmentation. Further insights into the molecular aspects of cytotoxicity of anatase-prevailing TiO2 NPs were obtained by comparative proteomics delineating that TiO2 NPs deregulate expression of a variety of proteins and associated pathways. This inevitably results in a decreased cellular ability to detoxify reactive oxygen species and respond to various stress conditions. The study provides novel data that add another piece to the jigsaw of the relation between structural features of NPs and biosafety.

Case study: Reinforcement of 45S5 bioglass robocast scaffolds by HA/PCL nanocomposite coatings.

The purpose of this study is to analyze the mechanical enhancement provided by nanocomposite coatings deposited on robocast 45S5 bioglass (BG) scaffolds for bone tissue regeneration. In particular, a nanocomposite layer consisting of hydroxyapatite (HA) nanoparticles, as reinforcing phase, in a polycaprolactone (PCL) matrix was deposited onto the surface of the BG struts conforming the scaffold. Three different HA nanopowders were used in this study. The effect of particle size and morphology of these HA nanopowders on the mechanical performance of 45S5 BG scaffolds is evaluated.