Optimization and kinetic modeling of waste lard methanolysis in a continuous reciprocating plate reactor

Continuous biodiesel production from a waste pig-roasting lard, methanol and KOH was carried out in a reciprocating plate reactor (RPR) using a factorial design containing three process factors, namely methanol/lard molar ratio, catalyst loading, and normalized height of the reactor. The main goals were to optimize the influential process factors with respect to biodiesel purity using the response surface methodology and to model the kinetics of the transesterification reaction in order to describe the change of triacylglycerols (TAG) and fatty acid methyl esters (FAME) concentrations along the RPR height. The first-order rate law was proved for both the reaction and the mass transfer. The model of the changing reaction mechanism and mass transfer of TAG was also applicable. Both kinetic models agreed with the experimental concentrations of TAG and FAME determined along the RPR height.     

Electrochemical properties of nanostructured Li1.2V3O8 in aqueous LiNO3 solution

The amorphous hydrated precursor of Li_1.2V₃O₈ was synthesized by soft chemistry method, and then heat-treated in air at several temperatures within the range 200–400 °C. The heat-treatment changed its morphological, structural and charging/discharging performance. The product obtained upon the treatment at 300 °C, consisting of uniform, rod-shaped particles, 100–150 nm in diameter and 300–800 nm in length, displayed the best electrochemical performance in aqueous LiNO₃ solution. Its initial discharge capacity amounted to 136.8 mAh g⁻¹ at a rate of C/5, which upon 50 charging/discharging cycles decreased for only 12%.     

Physicochemical and textural properties of puff pastry margarines

In this paper some physicochemical and textural characteristics of four puff pastry margarines are defined: MLT1 and MLT2 with low trans fatty acid (TFA) content, MLT3 with relatively low and MLT4 with high TFA content. Analyzing the solid trigliceride content (SFC), the crystallization kinetics in isothermal conditions and the margarine firmness, it is determined whether the technological characteristics of margarines (which are very important for puff pastry quality) are significantly changed due to TFA decrease in margarines. The highest SFC at 10, 20, 25 i 30°C have samples MLT1 and MLT4. Despite of significant differences in fatty acid composition of these margarines, SFC content at temperatures at 20, 25, and 30°C do not differ significantly, at the level of significance of 95% (p>0.05). The SFC of MLT1 and MLT2 samples, which have practically the same fatty acid composition at every investigated temperature, statistically have significant difference (p<0.05). The crystallization kinetics are in the range from 2.6 to 10.1% per min. The significance of the induction period at every observed samples is negligible. The average firmness of margarine samples MLT1, MLT2, MLT3, and MLT4 at 20, 25, and 30°C is significantly different (p<0.05). The firmness changes of the samples MLT1 and MLT2 in the most important temperature interval for puff pastry production (between 20 and 30°C) are at level of 5 to 25%, and for margarine samples MLT3 and MLT4 these values reach even 70%.     

The NaxMnO2 materials prepared by a glycine-nitrate method as advanced cathode materials for aqueous sodium-ion rechargeable batteries

Cathodic material for sodium-ion rechargeable batteries based on Na_xMnO₂ were synthesized by glycine nitrate method and subsequent annealing at high temperatures. Different crystal structures with different morphologies were obtained depending on the annealing temperature: hexagonal layeredα-Na_0.7MnO_2.05 nanoplates were obtained at 850 °C, while 3-D tunnel structured Na_0·4MnO₂ and Na_0·44MnO₂, both with rod-like morphology, were obtained at 800 °C and 900 °C, respectively. The investigations of the electrochemical behavior of obtained cathodic materials in aqueous NaNO₃ solution have shown that Na_0·44MnO₂ obtained at 900 °C has shown the best battery performance. Its initial discharge capacities are 123.5 mA h/g, 113.2 mA h/g, and 102.0 mA h/g at the high current densities of 1000, 2000 and 5000 mA/g, respectively.     

Grape Seed Oil Characterization: A Novel Approach for Oil Quality Assessment

The amount of organic pomace, left behind agricultural processes, is continuously rising in accordance with industrial progress. Grape pomace, generated in the wine industry all over the world, represents a raw material for obtaining valuable products. Grape seeds are especially rich in oil containing bioactive compounds that can have various health‐related effects. The aim of the study is to compare the quality of seed oils obtained from six white grapes, including two Serbian autochthonous varieties. Linoleic acid, associated with numerous health benefits, is the major fatty acid in all samples (≈66% of total); α‐tocopherol is the main tocopherol homologue. Total polyphenol content ranges from 73.4 to 104.3 mg of gallic acid equivalents per 100 g. In order to provide comprehensive information about antioxidant capacity of grape seed oil (GSO), three tests are performed (ferric ion reducing antioxidant power; 2,2’‐diphenyl‐1‐picrylhydrazyl, and 2,2’‐azino‐bis(3‐ethylbenzthiazoline‐6‐sulphonic acid) radical scavenging). Antimicrobial activity is investigated against different strains; however, GSO inhibits the growth of Staphylococcus aureus and Candida albicans. Obtained results are used to develop a novel approach for oil quality assessment. Calculated oil quality scores (OQS) reveal no significant difference between international and autochthonous varieties, although Smederevka stands out as the most potent one. Practical applications : Considering the progressive waste increase in the wine industry and keeping in mind all health‐promoting effects of grape seed oil (GSO), it is clearly observed that oil production represents a profitable and sustainable utilization of grape seeds. The results of the present study show that GSO is a rich source of compounds with antioxidant and antimicrobial properties. In addition, this work provides deeper insight into a quality of Serbian autochthonous grape varieties that are still insufficiently explored. Furthermore, the proposed oil quality score could be used as a comprehensive and unbiased method that enables quality assessment of oils. This tool can find practical application in comparing different plant oils regarding their compositional and functional properties. Finally, it would contribute to making some general oil intake recommendations.     

The gadolinium effect on crystallization behavior and luminescence of β-NaYF4:Yb,Er phase

Single phase β-NaY_0.8-xGd_xYb_0.18Er_0.02F₄ nanoparticles with different concentrations of gadolinium ions were prepared via PVP-assisted solvothermal treating at 200°C (PVP- polyvinylpyrrolidone). With the increase in Gd³⁺ concentration, size of the nanoparticles decreased. The up-converting spectra recorded upon 980 nm irradiation showed the green (510-560 nm) and red (640-690 nm) emissions, due to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions, respectively. The strongest up-conversion luminescence was detected in 15 mol% Gd³⁺-doped nanoparticles obtained after 20 hours of solvothermal treating. With the rise of Gd³⁺ content up-conversion emission decreased due to increased defect concentration in the NaYF₄ matrix. Fourier transform infrared spectroscopy proved in situ generation of hydrophilic nanoparticles as a result of PVP ligands retention at the particle surface.     

Evaluation of a model system for the selective study of the lipid peroxidation process

The effect of molecular environment on the peroxidation of linoleic acid (LA), a polyunsaturated fatty acid (PUFA), initiated by ferrous ions was investigated in acidic and neutral pH conditions. Mixed nonionic surfactants TWEEN®‐20/LA micelles were established as a model system to obtain a surfactant‐in‐lipid aqueous system at high acidity level. The peroxidation of LA was induced by ferrous ions and the kinetics of the produced conjugated dienes was followed by UV measurements and the ferric thiocynate method. Ferrous ions were oxidized only by the preformed LA hydroperoxides, which under established conditions produced lipid alkoxyl and peroxyl radicals as the sole initiators of propagation. The results revealed the LA peroxidation process remained mainly unaffected within the 2.5<pH<5.5 range, while highly pH sensitive around pH 7. The propagation process prevailed at optimal concentrations of 500 µM of LA and 280 µM TWEEN®‐20, and at the ferrous ion concentration up to 75 µM, irrespective of the buffer used. Practical applications: A simple model system in water, suitable for the selective study of the lipid peroxidation propagation phase induced by ferrous ion is presented here. Fatty acids serve as model compounds susceptible to processes associated with oxidative radical initiated‐modifications of lipids. The obtained results contribute to a better understanding of the oxidative behavior of lipids, particularly those soluble in nonionic surfactant micelles in acidic medium. The oxidative stability of the PUFA in model systems containing TWEEN®‐20 and ferrous ion at low pH could be predicted and controlled by measuring the lipid hydroperoxide formation. The experimental conditions presented may also provide a suitable system for the study of the termination phase of lipid peroxidation.     

Surface modification of anatase nanoparticles with fused ring catecholate type ligands: a combined DFT and experimental study of optical properties

Surface modification of nanocrystalline TiO(2) particles (45 ?) with catecholate-type ligands consisting of an extended aromatic ring system, i.e., 2,3-dihydroxynaphthalene and anthrarobin, was found to alter the optical properties of the nanoparticles in a similar way to modification with catechol. The formation of inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and the reduction of the band gap upon the increase of the electron delocalization on the inclusion of additional rings. The binding structures were investigated by FTIR spectroscopy. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of catecholate type (binuclear bidentate binding-bridging) thus restoring the six-coordinated octahedral geometry of surface Ti atoms. From the Benesi-Hildebrand plot, stability constants in methanol/water = 90/10 solutions at pH 2 of the order 10(3) M(-1) have been determined. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain vibrational frequencies of charge transfer complexes, and the calculated values were compared with the experimental data.     

Study on the interaction of Basic Violet 2 with hydroxypropyl-β-cyclodextrin

The formation of the inclusion complexes of Basic Violet 2 (New Fuchsin) with hydroxypropyl-β-cyclodextrin (HP-β-CD) was studied by UV-Vis absorption and fluorescence spectroscopy. The binding constants of the inclusion complexes, K_B, were obtained considering the maximum shift of the absorption spectra, the absorption areas deconvoluted as the sum of two gaussian constituents, the relative fluorescence quantum yield and the fluorescence maximum shift. The values achieved were 2.7 × 10³ M⁻¹, 0.95 × 10³ M⁻¹ and 2.8 × 10³ M⁻¹, 2.2 × 10³ M⁻¹, respectively. Ab-initio calculations using B3LYP/6-31G level of approach and the natural bond orbital (NBO) analysis were performed to gain a deeper understanding of the inclusion phenomena. The result showed a high complexation in aqueous media.     

Antitumor Mechanisms of Amino Acid Hydroxyurea Derivatives in the Metastatic Colon Cancer Model

The paper presents a detailed study of the biological effects of two amino acid hydroxyurea derivatives that showed selective antiproliferative effects in vitro on the growth of human tumor cell line SW620. Tested compounds induced cell cycle perturbations and apoptosis. Proteins were identified by proteomics analyses using two-dimensional gel electrophoresis coupled to mass spectrometry, which provided a complete insight into the most probable mechanism of action on the protein level. Molecular targets for tested compounds were analyzed by cheminformatics tools. Zinc-dependent histone deacetylases were identified as potential targets responsible for the observed antiproliferative effect.