Romana Cerc Korošec

Morphological, thermal, and structural aspects of dried and redispersed nanofibrillated cellulose (NFC)

Abstract The effects of various drying techniques, such as air, oven, freeze, and spray drying, on the morphological, thermal, and structural behaviors of two different nanofibrillated cellulose (NFC) materials were investigated. Field emission scanning electron microscopy (FE-SEM) observations indicated an interlaced network formation of predominantly in-plane fibrillar orientation for air- and oven-dried samples, while freeze and spray drying resulted in the formation of coarse and fine powder fractions. Comparison of redispersed powders obtained by freeze and spray drying indicated that aggregation phenomena are significantly reduced in freeze-dried specimens. Rheological and sedimentation analysis revealed that the freeze-dried NFC powders are more stable than spray-dried NFC powders when redispersed in water. Aggressive dehydration processes, such as freezing or heating, significantly influence the thermal stability of the dried cellulose samples. On the contrary, the crystallinity properties of dried NFC materials are very similar regardless of the drying treatment.

Transformation of hydrogen titanate nanoribbons to TiO2 nanoribbons and the influence of the transformation strategies on the photocatalytic performance.

Summary The influence of the reaction conditions during the transformation of hydrogen titanate nanoribbons to TiO2 nanoribbons on the phase composition, the morphology, the appearance of the nanoribbon surfaces and their optical properties was investigated. The transformations were performed (i) through a heat treatment in oxidative and reductive atmospheres in the temperature range of 400–650 °C, (ii) through a hydrothermal treatment in neutral and basic environments at 160 °C, and (iii) through a microwave-assisted hydrothermal treatment in a neutral environment at 200 °C. Scanning electron microscopy investigations showed that the hydrothermal processing significantly affected the nanoribbon surfaces, which became rougher, while the transformations based on calcination in either oxidative or reductive atmospheres had no effect on the morphology or on the surface appearance of the nanoribbons. The transformations performed in the reductive atmosphere, an NH3(g)/Ar(g) flow, and in the ammonia solution led to nitrogen doping. The nitrogen content increased with an increasing calcination temperature, as was determined by X-ray photoelectron spectroscopy. According to electron paramagnetic resonance measurements the calcination in the reductive atmosphere also resulted in a partial reduction of Ti4+ to Ti3+. The photocatalytic performance of the derived TiO2 NRs was estimated on the basis of the photocatalytic oxidation of isopropanol. After calcinating in air, the photocatalytic performance of the investigated TiO2 NRs increased with an increased content of anatase. In contrast, the photocatalytic performance of the N-doped TiO2 NRs showed no dependence on the calcination temperature. An additional comparison showed that the N-doping significantly suppressed the photocatalytic performance of the TiO2 NRs, i.e., by 3 to almost 10 times, in comparison with the TiO2 NRs derived by calcination in air. On the other hand, the photocatalytic performance of the hydrothermally derived TiO2 NRs was additionally improved by a subsequent heat treatment in air.

Encapsulation of (−)‐epigallocatechin gallate into liposomes and into alginate or chitosan microparticles reinforced with liposomes

BACKGROUND (-)-Epigallocatechin gallate (EGCG) was encapsulated into liposomes that were further incorporated into alginate and chitosan microparticles. The stability of free and encapsulated EGCG in all three systems was evaluated at different pH values and in fruit nectar. Furthermore, the interactions between EGCG and the compounds of the microparticles were studied using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). RESULTS All three encapsulation systems showed high encapsulation efficiency (>97%) and sustained release; in 14 days, no more than 15% of EGCG was released. The encapsulation systems successfully protected EGCG against degradation at alkaline pH. For non-encapsulated EGCG, >70% was degraded after 14 days, while there was no significant degradation of encapsulated EGCG in these three systems. In fruit nectar, >30% of non-encapsulated EGCG was degraded in 14 days, while only 6% of EGCG encapsulated into liposomes or chitosan microparticles reinforced with liposomes was degraded at that time. The DSC and FTIR analyses showed that the main interactions occurred between the liposomes and the EGCG. CONCLUSION This study demonstrates that liposomes as well as alginate and chitosan microparticles reinforced with liposomes have the potential to enhance EGCG stability in food products during storage.

Sulfur-, nitrogen- and platinum-doped titania thin films with high catalytic efficiency under visible-light illumination

Titanium dioxide photocatalysts have received a lot of attention during the past decades due to their ability to degrade various organic pollutants to CO2 and H2O, which makes them suitable for use in environmental related fields such as air and water treatment and self-cleaning surfaces. In this work, titania thin films and powders were prepared by a particulate sol–gel route, using titanium tetrachloride (TiCl4) as a precursor. Afterwards, the prepared sols were doped with nitrogen (ammonium nitrate, urea), sulfur (thiourea) and platinum (chloroplatinic acid), coated onto glass substrates by dip-coating, and thermally treated in a muffle furnace to promote crystallization. The resulting thin films were then characterized by various techniques (i.e., TGA-DSC-MS, XRD, BET, XPS, SEM, band gap measurements). The photocatalytic activity of the prepared thin films was determined by measuring the degradation rate of plasmocorinth B (PB), an organic pigment used in the textile industry, which can pose an environmental risk when expelled into wastewater. A kinetic model for adsorption and subsequent degradation was used to fit the experimental data. The results have shown an increase in photocatalytic activity under visible-light illumination of nonmetal and metal doped and co-doped titania thin films compared to an undoped sample.

Structural properties and thermal stability of cobalt- and chromium-doped α-MnO2 nanorods

α-MnO2 nanorods were synthesized via the hydrothermal decomposition of KMnO4 in an acidic environment in the presence of Co2+ and Cr3+ ions. Reactions were carried out at three different temperatures: 90, 130 and 170 °C. All prepared samples exhibit a tetragonal MnO2 crystalline phase. SEM–EDS analysis shows that cobalt cations are incorporated to a higher degree into the MnO2 framework than chromium ions, and that the content of the dopant ions decreases with increasing reaction temperature. The oxidation of Co2+ to Co3+ during the reaction was proved by an XANES study, while EXAFS results confirm that both dopant ions substitute Mn4+ in the center of an octahedron. The K/Mn ratio in the doped samples synthesized at 170 °C is significantly lower than in the undoped samples. Analysis of an individual cobalt-doped α-MnO2 nanorod with HAADF-STEM reveals that the distribution of cobalt through the cross-section of the nanorod is uniform. The course of thermal decomposition of the doped nanorods is similar to that of the undoped ones. Dopant ions do not preserve the MnO2 phase at higher temperatures nor do they destabilize the cryptomelane structure.

Synthesis and characterization of cobalt acrylate–melamine co-crystals

A new co-crystal of tetraaqua acrylato cobalt (II) complex and melamine, [Co(acr)2(H2O)4]·4MA·2DMF (acr = acrylate, MA = melamine, DMF = dimethylformamide), has been synthesized and characterized using IR, UV-Vis, thermogravimetric analysis, and single-crystal X-ray diffraction. The complex contains discrete unities of [Co(acr)2(H2O)4], melamine, and DMF linked by hydrogen bonds. Investigations evidenced that Co(II) has an octahedral stereochemistry and both acrylate ions present unidentate coordination mode. Thermal decomposition occurs in four steps and denotes that melamine is lost at high temperatures, and this indicates a greater stability that may be associated with the presence of hydrogen bonds network.