New insights into the functionalization of multi-walled carbon nanotubes with aniline derivatives

Multi-walled carbon nanotubes (MWCNT) were functionalized with a variety of chemical groups by reaction of p-substituted anilines (R–Ph–NH₂) in the presence and absence of isopentyl nitrite used for the in situ generation of diazonium species. All materials were characterized by X-ray photoelectron spectroscopy, thermogravimetry and infrared spectroscopy.In the presence of isopentyl nitrite, the extent of functionalization was high and nearly independent on the amount of isopentyl nitrite and on the aniline substituents (R = F, Cl, I, NH₂, NO₂, OH, COOH, COOEt and Et). Unexpectedly, the functionalization of MWCNT with anilines bearing electron withdrawing groups was also observed in the absence of isopentyl nitrite. In the case of OH–Ph–NH₂, the reaction leads to MWCNT with the highest degree of functionalization and this can be considered as a new and efficient methodology for CNT functionalization with phenol groups. The overall reaction mechanism is discussed for both reaction conditions: confirmation of a radical chain mechanism was obtained for the reaction performed in the presence of isopentyl nitrite, while the formation of stabilized dipolar intermediate species seems to be involved in the absence of isopentyl nitrite. The materials with the highest degree of functionalization showed very good dispersions in acetonitrile even after 1 month.     

Supercritical Fluid Extraction of Eucalyptus globulus Bark-A Promising Approach for Triterpenoid Production

Eucalyptus bark contains significant amounts of triterpenoids with demonstrated bioactivity, namely triterpenic acids and their acetyl derivatives (ursolic, betulinic, oleanolic, betulonic, 3-acetylursolic, and 3-acetyloleanolic acids). In this work, the supercritical fluid extraction (SFE) of Eucalyptus globulus deciduous bark was carried out with pure and modified carbon dioxide to recover this fraction, and the results were compared with those obtained by Soxhlet extraction with dichloromethane. The effects of pressure (100-200 bar), co-solvent (ethanol) content (0, 5 and 8% wt), and multistep operation were studied in order to evaluate the applicability of SFE for their selective and efficient production. The individual extraction curves of the main families of compounds were measured, and the extracts analyzed by GC-MS. Results pointed out the influence of pressure and the important role played by the co-solvent. Ethanol can be used with advantage, since its effect is more important than increasing pressure by several tens of bar. At 160 bar and 40 °C, the introduction of 8% (wt) of ethanol greatly improves the yield of triterpenoids more than threefold.     

Drying of Pastes in Vibro-Fluidized Beds: Effects of the Amplitude and Frequency of Vibration

Abstract

The dimensionless vibration number (Γ) is the parameter most widely applied to quantify the vibration energy of a vibro-fluidized bed. It is defined as a function of the amplitude (A) and of the frequency of vibration (f). Most works in literature present their results as a function of Γ, which is adopted as a single parameter to explain the results on fluid dynamic behavior of vibro-fluidized beds, independent on the magnitudes of A and f. From its definition, however, it is possible to obtain identical values of Γ just by combining different values of A and f, and further studies are necessary for a better analysis of fluid dynamic behavior of vibro-fluidized beds concerning their vibration energy. Therefore, in this work the effects of dimensionless vibration number on the fluid dynamic behavior of a vibro-fluidized bed will be investigated by choosing different combinations of A and f values arranged to provide identical values of Γ. The tests were carried out for dry and wet beds, for values of Γ = 0.0 (fluidized bed), 1.0, 2.0, and 4.0. The results indicate that Γ must be used carefully when applied as the only parameter to characterize the vibration effects in a vibro-fluidized bed since very different fluid dynamic behavior was detected at a fixed Γ at different amplitudes and frequencies.     

Moisture Prediction During Paste Drying in a Spouted Bed

The objective of this work was to derive and experimentally verify a hybrid CST/neural network model to determine the moisture content of the powders produced during paste drying in a spouted bed and describe the highly coupled heat and the mass transfer. The model was derived from overall energy and mass balances with effective drying kinetics given by a neural network. Simulations were performed in MatLab and drying experiments for model verification were carried out for different pastes in a conical, semi-pilot-scale spouted bed.     

Experimental design of the kinetic resolution of a key precursor of high‐value bioactive myo‐inositols by an immobilized lipase

BACKGROUND: The response surface methodology was successfully applied to the optimization of the reaction variables for the kinetic resolution of a precursor of high‐value myo‐inositols, ( ± )‐1,2‐O‐isopropylidene‐3,6‐di‐O‐benzyl‐myo‐inositol (( ± )‐1), by Novozym 435. The resolutions were run separately, with two acylating agents, ethyl acetate and vinyl acetate, in a solvent‐free system. The variables analyzed were reaction temperature, substrate concentration, water concentration and enzyme activity. A statistical model was employed for the evaluation of the influence of the variables on conversion and enantiomeric excess (ee). RESULTS: The optimal conditions for this resolution using vinyl acetate as acylating agent were 45 °C, 5 mg mL^?1 of substrate, 71 U of enzyme activity and 0%w/w of water concentration. The high conversion (49.2 %) and ee (>99%) reached in the chemoenzymatic synthesis of acylated product, L‐(?)‐5‐O‐Acetyl‐3,6‐di‐O‐benzyl‐1,2‐O‐isopropylidene‐myo‐inositol, secure the efficient synthesis of the D enantiomorph present in the original racemic mixture (( ± )‐1) as well. CONCLUSIONS: The use of the experimental design strategy was productive, leading to a 14‐fold increase in the productivity of the reaction compared with the non‐optimized conditions. Both derivative L‐(?)‐2 and remaining substrate D‐(+)‐1 were obtained at high ee. © 2012 Society of Chemical Industry     

Specific interactions in blends containing Chitosan and functionalized polymers. Molecular dynamics simulations

Chitosan (CS)/poly(vinyl alcohol) (PVA) and Chitosan/poly(2-hydroxyethyl methacrylate) (P2HEM) blends have been studied through molecular dynamic simulations. In a previous work it was found miscibility between these polymers and it was attributed to hydrogen bonding formation. However, the experimental information obtained was not enough to know which of the interacting groups of Chitosan, i.e. -CH₂OH or -NH₂, are responsible of the interaction. Therefore, we have performed molecular dynamics simulation runs of 1 ns in order to calculate radial distribution functions (RDF) for the groups tentatively involved in the interaction. The results are correlated with our previous experimental data. This way, we have obtained a more precise conclusive information about the interactions involved as function of the blends composition. For low compositions of PVA and P2HEM the interaction is predominantly with the hydroxymethyl groups of CS while as the composition of PVA and P2HEM increases, the interaction with the amine groups increases.     

Bio-based sustainable films from the Algerian Opuntia ficus-indica cladodes powder: Effect of plasticizer content

The present study investigated the fabrication and characterization of bio-based sustainable films composed of a terrestrial plant raw material, namely Opuntia ficus-indica (OFI) cladodes powder (CP) and a marine seaweed derivative, namely agar (A). The effect of glycerol concentration on the properties of the casted films was evaluated at four different contents, namely 30, 40, 50 and 60 wt%. The films present UV-blocking properties, as well as moderate mechanical performance, thermal stability, and water vapor transmission rate (WVTR). The results point to an increase in thickness, elongation at break, moisture content, water solubility, and WVTR with increasing glycerol content. On the contrary, Young's modulus, tensile strength, and water contact angle decreased as glycerol concentration increased. The best combination is obtained for the film with 30% glycerol, based on an intermediate compromise between physical, mechanical, thermal, and barrier properties. All these outcomes express the potentiality of the powder obtained from grinding the OFI cladodes as raw material to produce low-cost films for the development of sustainable packaging materials.     

Growth of carbon nanotube forests on carbon fibers with an amorphous silicon interface

Aligned multi-walled carbon nanotube forests were grown by chemical vapour deposition on carbon fibers by the use of an amorphous Si interface. The Si layer creates a barrier, hindering the Fe catalyst diffusion into the carbon fibers. This method provides a way to tailor the thermal, electrical and mechanical properties of the fiber-resin interface of a polymer composite.     

Immunomodulatory Properties of Umbilical Cord Blood-Derived Small Extracellular Vesicles and Their Therapeutic Potential for Inflammatory Skin Disorders

Umbilical cord blood (UCB) has long been seen as a rich source of naïve cells with strong regenerative potential, likely mediated by paracrine signals. More recently, small extracellular vesicles (sEV), such as exosomes, have been shown to play essential roles in cell-to-cell communication, via the transport of numerous molecules, including small RNAs. Often explored for their potential as biomarkers, sEV are now known to have regenerative and immunomodulating characteristics, particularly if isolated from stem cell-rich tissues. In this study, we aim to characterize the immunomodulating properties of umbilical cord blood mononuclear cell-derived sEV (UCB-MNC-sEV) and explore their therapeutic potential for inflammatory skin diseases. UCB-MNC-sEV were shown to shift macrophages toward an anti-inflammatory phenotype, which in turn exert paracrine effects on fibroblasts, despite previous inflammatory stimuli. Additionally, the incubation of PBMC with UCB-MNC-sEV resulted in a reduction of total CD4⁺ and CD8⁺ T-cell proliferation and cytokine release, while specifically supporting the development of regulatory T-cells (Treg), by influencing FOXP3 expression. In a 3D model of psoriatic skin, UCB-MNC-sEV reduced the expression of inflammatory and psoriatic markers IL6, IL8, CXCL10, COX2, S100A7, and DEFB4. In vivo, UCB-MNC-sEV significantly prevented or reversed acanthosis in imiquimod-induced psoriasis, and tendentially increased the number of Treg in skin, without having an overall impact on disease burden. This work provides evidence for the anti-inflammatory and tolerogenic effect of UCB-MNC-sEV, which may be harnessed for the treatment of Th17-driven inflammatory skin diseases, such as psoriasis.     

Performance of anaerobic bioreactor treating fish-processing plant wastewater pre-hydrolyzed with a solid enzyme pool

The effect of a lipase-rich enzyme preparation produced by the fungus Penicillium simplicissimum on solid-state fermentation was evaluated in a 4.9 L up-flow anaerobic sludge blanket bioreactor (UASB) treating fish-processing plant wastewater containing 1500 mg oil and grease (O&G)/L. The oil and grease hydrolysis step was carried out with 0.5% or 0.2% (w/v) of the solid enzyme preparation (SEP) at 30 °C for 8 h. The bioreactor operated at 30 °C with a hydraulic retention time of 10 h for a period of over 100 days, showed high total COD removal efficiencies (85.3% for 0.5% SEP and 90.9% for 0.2% SEP), when fed with pre-hydrolyzed wastewater, compared to a Control bioreactor fed with raw wastewater (79.9%). The Control bioreactor also showed high oil and grease accumulation in the biomass throughout the operational period (the O&G content reached 1.7 times that found in the inoculum of the UASB bioreactor), intensive scum formation, and several episodes of cessation of treatment to clean the three-phase separator. Thus it can be concluded that the enzyme pre-hydrolysis step together with anaerobic treatment of the fish-processing plant wastewater improved the quality of the treated effluent and reduced operational problems.