Dispersing hydrophilic nanoparticles in hydrophobic polymers: HDPE/ZnO nanocomposites by a novel template-based approach

The efficiency of a novel template-based approach for the dispersion of hydrophilic nanoparticles within hydrophobic polymer matrices is investigated. The procedure envisages the permeation of a well dispersed nanoparticle suspension inside a micro-porous matrix, obtained through selective extraction of a sacrificial phase from a finely interpenetrated co-continuous polymer blend. Specifically, a blend of high density polyethylene (HDPE) and polyethylene oxide (PEO) at 50/50 wt% is prepared by melt mixing. The addition of small amounts of organo-clay promotes the necessary refinement of the blend morphology. Once removed the PEO, the micro-porous HDPE matrix is dipped in a colloidal suspension of zinc oxide nanoparticles which exhibits low interfacial tension with HDPE. A system prepared by traditional melt mixing is used as reference. Melt- and solid-state viscoelastic measurements reveal a good quality of the filler dispersion despite the uneven distribution on micro-scale. The latter can be capitalized to minimize the filler content to attain a certain improvement of the material properties or to design nano-structured polymer composites. © BME-PT

Improving osteoblasts cells proliferation via femtosecond laser surface modification of 3D-printed poly-ε-caprolactone scaffolds for bone tissue engineering applications

Synthetic polymer biomaterials incorporating cells are a promising technique for treatment of orthopedic injuries. To enhance the integration of biomaterials into the human body, additional functionalization of the scaffold surface should be carried out that would assist one in mimicking the natural cellular environment. In this study, we examined poly-epsilon-caprolactone (PCL) fiber matrices in view of optimizing the porous properties of the constructs. Altering the porosity of a PCL scaffold is expected to improve the material's biocompatibility, thus influencing its osteoconductivity and osteointegration. We produced 3D poly-epsilon-caprolactone (PCL) matrices by a fused deposition modeling method for bone and cartilage tissue engineering and performed femtosecond (fs) laser modification experiments to improve the surface properties of the PCL construct. Femtosecond laser processing is one of the useful tools for creating a vast diversity of surface patterns with reproducibility and precision. The processed surface of the PCL matrix was examined to follow the effect of the laser parameters, namely the laser pulse energy and repetition rate and the number (N) of applied pulses. The modified zones were characterized by scanning electron microscopy (SEM), confocal microscopy, X-ray computed tomography and contact angle measurements. The results obtained demonstrated changes in the morphology of the processed surface. A decrease in the water contact angle was also seen after fs laser processing of fiber meshes. Our work demonstrated that a precise control of material surface properties could be achieved by applying a different number of laser pulses at various laser fluence values. We concluded that the structural features of the matrix remain unaffected and can be successfully modified through laser postmodification. The cells tests indicated that the micro-modifications created induced MG63 and MC3T3 osteoblast cellular orientation. The analysis of the MG63 and MC3T3 osteoblast attachment suggested regulation of cells volume migration

White-etching matter in bearing steel. Part II: Distinguishing cause and effect in bearing steel failure

The premature failure of large bearings of the type used in wind turbines, possibly through a mechanism called “white-structure flaking”, has triggered many studies of microstructural damage associated with “white-etching areas” created during rolling contact fatigue, although whether they are symptoms or causes of failure is less clear. Therefore, some special experiments have been conducted to prove that white-etching areas are the consequence, and not the cause, of damage. By artificially introducing a fine dispersion of microcracks in the steel through heat treatment and then subjecting the sample to rolling contact fatigue, manifestations of hard white-etching matter have been created to a much greater extent than samples similarly tested without initial cracks. A wide variety of characterization tools has been used to corroborate that the white areas thus created have the same properties as reported observations on real bearings. Evidence suggests that the formation mechanism of the white-etching regions involves the rubbing and beating of the free surfaces of cracks, debonded inclusions, and voids under repeated rolling contact. It follows that the focus in avoiding early failure should be in enhancing the toughness of the bearing steel in order to avoid the initial microscopic feature event.Funding by CONACyT, the Cambridge Overseas Trust, and the Roberto Rocca Education Programme is highly appreciated and acknowledged.This is the accepted manuscript version. The final published version is available from Springer at http://link.springer.com/article/10.1007%2Fs11661-014-2431-x

The influence of immersion sonication, contact sonication and pulsed electric field treatment on the electrical conductivity of carrot tissue

Celem pracy była analiza wpływu sonikacji (US) immersyjnej i kontaktowej oraz obróbki pulsacyjnym polem elektrycznym (PEF) na przewodność elektryczną. Określono także zawartość suchej substancji w materiale poddanym obróbce US oraz PEF. W przypadku obróbki pulsacyjnym polem elektrycznym natężenie pola elektrycznego wynosiło 0,3 lub 5 kV·cm–1, liczba impulsów 0–100, a właściwe zużycie energii 0–80 kJ·kg–1. Aplikacja pulsacyjnego pola elektrycznego prowadzi do wzrostu przewodności elektrycznej analizowanej tkanki roślinnej. Największy wzrost tego parametru zanotowano w przypadku zastosowania natężenia 3 kV·cm–1 oraz aplikacji 100 impulsów. Obróbka tkanki marchwi pulsacyjnym polem elektrycznym skutkowała także wzrostem zawartości suchej substancji w porównaniu z materiałem niepotraktowanym PEF, co wiązało się z wyciekiem wody z materiału w wyniku elektroporacji. Z kolei wpływ sonikacji na przewodność elektryczną oraz zawartość suchej substancji był niejednoznaczny i prowadził, w zależności od zastosowanych parametrów, do wzrostu lub obniżenia wartości tych parametrów. W tym przypadku, na ogół, największe zmiany zanotowano w próbkach poddanych obróbce kontaktowej.The aim of this work was to analyze the influence of sonication (US) and pulsed electric field treatment on the electrical conductivity and dry matter content of the carrot tissue. The sonication was performed by contact (26 kHz) and immersion method (21 and 40 kHz). Ultrasounds application lasted 0, 5, 10, 20, 30 min at 100% duty cycle and 60 min at 50% duty cycle. The electric field intensity of PEF was equal to 0, 3 and 5 kV·cm–1, the number of pulses varied from 0 to 100 and the specific energy input from 0 to 80 kJ·kg–1. The application of PEF resulted in the increase of the electrical conductivity(EC) of the plant tissue from 32.67 to 199.67–344.43 μS·cm–1, in the case of intact and PEF treated samples, respectively. The highest value of the electrical conductivity was observed in the material treated by 3 kV·cm–1 and 100 pulses. The PEF treatment caused the increase of dry matter content (from 0.0957 to 0.1172–0.1258 kg·kg–1), which could be linked to the cell membrane rupture and water leakage due to the electroporation phenomenon. However, the increase of pulse number from 10 to 100 at constant (5 kV·cm–1) electric field intensity did not increase the dry matter content. The impact of sonication on the both electrical conductivity and dry matter content was ambiguous. The sonication carried out by immersion method in both frequencies for 0–30 min did not change the electrical conductivity significantly. The statistically relevant differences were stated only in the case of treatment which lasted 60 min at 50% duty cycle. The contact sonication caused the biggest changes of electrical conductivity in comparison to the untreated material. The highest EC was observed in the case of sample sonicated for 30 min (47.80 μS·cm–1). However, in the case of samples treated by contact method for 20 and 60 min the differences in comparison with the intact carrot were irrelevant. Samples treated by immersion method were characterized by lower dry matter content whereas carrot treated by contact method exhibited higher values of dry matter content in comparison to the intact tissue. Such behavior probably was correlated with the evaporation in the case of contact US-treated samples (surrounded by air during the sonication) and leakage to the water, in the case of immersion US processed material

Nanoparticles doped with TM and RE ions for applications in optoelectronics

Nanoparticles of wide band gap compounds, when doped with rare earth or transition metal ions, are perspective candidates for efficient phosphors in a new generation of light sources for an overhead illumination, i.e., in compact fluorescence lamps and in semiconductor-based white light emitting diodes. Mechanisms of emission enhancement in doped nanoparticles are discussed based on the relevant experimental results. Mechanisms observed are due to carrier confinement, n-type co-doping, due to surface plasmons generation and super radiance.6 page(s

Nanoformulation Composed of Ellagic Acid and Functionalized Zinc Oxide Nanoparticles Inactivates DNA and RNA Viruses

The COVID-19 pandemic has strongly impacted daily life across the globe and caused millions of infections and deaths. No drug therapy has yet been approved for the clinic. In the current study, we provide a novel nanoformulation against DNA and RNA viruses that also has a potential for implementation against COVID-19. The inorganic–organic hybrid nanoformulation is composed of zinc oxide nanoparticles (ZnO NPs) functionalized with triptycene organic molecules (TRP) via EDC/NHS coupling chemistry and impregnated with a natural agent, ellagic acid (ELG), via non-covalent interactions. The physicochemical properties of prepared materials were identified with several techniques. The hybrid nanoformulation contained 9.5 wt.% TRP and was loaded with up to 33.3 wt.% ELG. ELG alone exhibited higher cytotoxicity than both the ZnO NPs and nanoformulation against host cells. The nanoformulation efficiently inhibited viruses, compared to ZnO NPs or ELG alone. For H1N1 and HCoV-229E (RNA viruses), the nanoformulation had a therapeutic index of 77.3 and 75.7, respectively. For HSV-2 and Ad-7 (DNA viruses), the nanoformulation had a therapeutic index of 57.5 and 51.7, respectively. In addition, the nanoformulation showed direct inactivation of HCoV-229E via a virucidal mechanism. The inhibition by this mechanism was > 60%. Thus, the nanoformulation is a potentially safe and low-cost hybrid agent that can be explored as a new alternative therapeutic strategy for COVID-19

Transition metals in ZnO nanocrystals: Magnetic and structural properties

Currently, wide-gap ZnO nanoparticles bear important potential application in electro-optical devices, transparent ultraviolet protection films, and spintronic devices. We have studied the magnetic properties of nanocrystals of ZnO(Fe, Co, Mn) prepared by two methods of synthesis. We have used the microwave assisted hydrothermal synthesis and traditional wet chemistry method followed by calcination. The detailed structural characterization was performed by means of X-ray diffraction and micro-Raman spectroscopy measurements. The morphology of the samples was studied by means of SEM and TEM microscopy. The results of systematic measurements of AC magnetic susceptibility as a function of temperature and frequency as well as SQUID magnetization are presented. The SQUID magnetization measurements revealed a clear bifurcation of the FC and ZFC plots. Such behavior suggested superparamagnetic behavior above the blocking temperature. The dynamic magnetic measurements were performed at small AC magnetic field with amplitude not exceeding 5 Oe and different frequency values (from 7 Hz to 9970 Hz). For ZnO(Fe) and ZnO(Mn), the AC susceptibility maxima has been found for in-phase susceptibility Re(χ) and for out of phase susceptibility Im(χ). We analyzed the observed frequency dependence of the peak temperature in the AC susceptibility curve using the empirical parameter Φ that is a quantitative measure of the frequency shift and is given by the relative shift of the peak temperature per decade shift in frequency, as well as Vogel- Fulcher law. We observed two different types of magnetic behavior, spin-glasslike behavior or superparamagnetic behavior, depending on the synthesis process. For ZnO(Co) nanocrystalline samples high temperature Curie-Weiss behavior in AC magnetic susceptibility was observed. We observed that the determined negative values of the Curie- Weiss temperature θ depend strongly on the nominal content of cobalt oxide. It was shown that for calcination method the values of θ increase with the increase of magnetic ion content indicating enhancement of predominance of antiferromagnetic interactions. For hydrothermal method the opposite effect was observed indicating the breakdown of predominance of aniferromagnetic coupling with the increase of nominal magnetic ion content. This paper gives an in-depth discussion of the structural and magnetic properties of ZnO nanocrystals in addition to the technological issues such as different methods of wet chemical synthesis

Synthesis and characterization of precipitation hardened amorphous matrix composite by mechanical alloying and pulse plasma sintering of Al<SUB>65</SUB>Cu<SUB>20</SUB>Ti<SUB>15</SUB>

This study reports synthesis of Al65Cu20Ti15 amorphous alloy by mechanical alloying and consolidation of the powder mass by pulsed plasma sintering. During sintering, several intermetallic phases precipitate from the amorphous matrix and cause a significant increase in nano-hardness and elastic modulus. Microstructure in as-milled and sintered conditions was characterized by X-ray diffraction, scanning/transmission electron microscopy and differential scanning calorimetric. Among various conditions of sintering, the composites pulse plasma, sintered at 500&#176;C, show the high compression strength (1745 MPa) and high indentation fracture toughness (4.96 MPa m&#189; ); although, the maximum density (3.73 Mg/in3), nano-hardness (14 GPa) and Young's modulus (208 GPa) in the present alloy have been obtained in the composites pulse plasma sintered at 600&#176;C

Highly biocompatible, nanocrystalline hydroxyapatite synthesized in a solvothermal process driven by high energy density microwave radiation

Dariusz Smolen1, Tadeusz Chudoba1, Iwona Malka1, Aleksandra Kedzierska1, Witold Lojkowski1, Wojciech Swieszkowski2, Krzysztof Jan Kurzydlowski2, Malgorzata Kolodziejczyk-Mierzynska3, Malgorzata Lewandowska-Szumiel31Polish Academy of Science, Institute of High Pressure Physics, Warsaw, Poland; 2Faculty of Materials Engineering, Warsaw University of Technology, Warsaw, Poland; 3Department of Histology and Embryology, Center of Biostructure Research, Medical University of Warsaw, Warsaw, PolandAbstract: A microwave, solvothermal synthesis of highly biocompatible hydroxyapatite (HAp) nanopowder was developed. The process was conducted in a microwave radiation field having a high energy density of 5 W/mL and over a time less than 2 minutes. The sample measurements included: powder X-ray diffraction, density, specific surface area, and chemical composition. The morphology and structure were investigated by scanning electron microscopy as well as transmission electron microscopy (TEM). The thermal behavior analysis was conducted using a simultaneous thermal analysis technique coupled with quadruple mass spectrometry. Additionally, Fourier transform infrared spectroscopy tests of heated samples were performed. A degradation test and a biocompatibility study in vitro using human osteoblast cells were also conducted. The developed method enables the synthesis of pure, fully crystalline hexagonal HAp nanopowder with a specific surface area close to 240 m2/g and a Ca/P molar ratio equal to 1.57. TEM measurements showed that this method results in particles with an average grain size below 6 nm. A 28-day degradation test conducted according to the ISO standard indicated a 22% loss of initial weight and a calcium ion concentration at 200 &amp;micro;mol/dm3 in the tris(hydroxymethyl)aminomethane hydrochloride test solution. The cytocompatibility of the obtained material was confirmed in a culture of human bone derived cells, both in an indirect test using the material extract, and in direct contact. A quantitative analysis was based on the 2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide. Viability assay as well as on DNA content measurements in the PicoGreen test. Indirect observations were performed at one point in time according to the ISO standard for in vitro cytotoxicity (ie, after 24 hours of cell exposure to the extracts). The direct contact tests were completed at three time points: after 24 hours, on day 7, and on day 14 of a culture in an osteogenic medium. All of the tests revealed good tolerance of cells toward the material; this was also shown by means of live/dead fluorescent staining. Both quantitative results and morphological observations revealed much better cell tolerance toward the obtained HAp compared to commercially available HAp NanoXIM, which was used as a reference material.Keywords: bone regeneration, bone substitute, microwave, HA