Integrated management of residues from tomato production: Recovery of value-added compounds and biogas production in the biorefinery context.

The biorefinery approach must be boosted in the management of agro-residues in the future. The present study aims to investigate the valorization of tomato production residues, namely rotten tomato (unfit for consumption - RT), green tomato (GT), and tomato branches (TB). The assessment involves the recovery of value-added compounds through the extraction process followed by biogas production through anaerobic digestion. A thorough characterization of the three residues (RT, GT, and TB) was carried out, including the identification of volatile compounds by solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS). The volatiles analysis revealed the presence of flavor enhancer compounds and molecules with insecticidal properties. A solid-liquid extraction with ethanol allowed the recovery of value-added compounds in the extracts, in particular phenolic compounds, ß-carotene, and lycopene, which contributed to the antioxidant activity. RT and TB extracts were found to be richer in total phenolic compounds (~27 mg GAE/gdb dry basis) and exhibited higher antioxidant activity (IC50 = 0.911 and 0.745 mg/mL). The tomato branches extract had the highest concentration of carotenoids with 37.23 and 3.08 mg/kgdb of ß-carotene and lycopene, respectively. The biochemical methane potential (BMP) was assessed in sealed reactors operating in anaerobic conditions for all the raw (RT, GT, and TB) and extracted substrates waste (RTe, GTe, and TBe). While the BMP of RT and GT was in the range of 232-285 mL CH4/g VS, a lower value of 141 mL CH4/g VS was obtained for TB. The methane production for each pair of raw and extracted substrates (RT/RTe, GT/GTe, and TB/TBe) was considered statistically similar at a 95 % confidence level. Overall, the value-added compounds recovery through ethanolic extraction did not compromise the methane production of the materials.

Multifactor analysis on the effect of collagen concentration, cross-linking and fiber/pore orientation on chemical, microstructural, mechanical and biological properties of collagen type I scaffolds.

This work evaluates the effect of processing variables on some physicochemical and mechanical properties of multi- and unidirectional laminar collagen type I scaffolds. The processing variables considered in this study included microstructure orientation (uni- and multidirectional fiber/pore controlled by freeze-drying methodology), cross-linking (chemical - using genipin and glutaraldehyde, and physical - using a dehydrothermal method), and collagen concentration (2, 5 and 8mg/ml). The biocompatibility of the scaffolds obtained in each of the evaluated manufacturing processes was also assessed. Despite previous research on collagen-based platforms, the effects that these processing variables have on the properties of collagen scaffolds are still not completely understood. Unidirectional scaffolds presented higher resistance to failure under stress than multidirectional ones. The cross-linking degree was found to decrease when the concentration of collagen increased whilst using chemical cross-linkers, and to increase with the concentration of collagen for the dehydrothermal cross-linked scaffolds. Pore orientation indexes of both unidirectional and multidirectional scaffolds were not influenced by collagen concentration. Cross-linked scaffolds were more hydrophobic than non-cross-linked ones, and presented water vapor permeability adequate for use in low-to-moderate exuding wounds. Pore size ranges were compatible with cell in-growth, independently of the employed cross-linking and freezing methodologies. Moreover, scaffolds cross-linked with glutaraldehyde presented higher in-growth of primary oral mucosa fibroblasts than those cross-linked with genipin or with the dehydrothermal treatment. This multi-factor analysis is expected to contribute to the design of collagen type I platforms, which are usable on several potential soft tissue-engineering applications.

Toxicity of the bionematicide 1,4-naphthoquinone on non-target soil organisms.

The main goal of the present study was to evaluate the ecotoxicological effects of 1,4-naphthoquinone (1,4-NTQ), a natural-origin compound presenting nematicidal activity, that can be obtained from walnut husk, in plants and soil invertebrates, including non-target soil nematode communities. This research was part of an ongoing project that aims to develop environmentally-friendly nematicides obtained from agricultural residues. The battery of ISO tests included emergence and growth of corn (Zea mays) and rape (Brassica napus); avoidance with the earthworm Eisenia andrei and the collembolan Folsomia candida; and reproduction with the previous species plus the enchytraeid Enchytraeus crypticus. A novel soil nematode community assay was also performed. ISO tests and nematode assays were conducted using a natural uncontaminated soil that was spiked with a range of 1,4-NTQ concentrations. Toxicity of 1,4-NTQ was found for all test-species and the most sensitive were F. candida and E. andrei. After 7 days of exposure to 1,4-NTQ, nematode abundance decreased along the concentration gradient, and a partial recovery was observed after 14 days (1,4-NTQ <48 mg kg-1 soil). The number of nematode families consistently decreased in both periods. Overall, results indicate that a 1,4-NTQ concentration of <20 mg kg-1 could be environmentally safe but preliminary data suggest that it might be ineffective for the target-nematodes, root-knot nematodes, Meloidogyne spp., and root-lesion nematodes, Pratylenchus spp. In addition, if higher dosages of 1,4-NTQ bionematicide are necessary, the potential recovery of non-target organisms under real field scenarios also needs to be assessed.

Dexamethasone-loaded poly(ε-caprolactone)/silica nanoparticles composites prepared by supercritical CO2 foaming/mixing and deposition.

A supercritical carbon dioxide (scCO2)-assisted foaming/mixing method (SFM) was implemented for preparing dexamethasone (DXMT)-loaded poly(ε-caprolactone)/silica nanoparticles (PCL/SNPs) composite materials suitable for bone regeneration. The composites were prepared from PCL and mesoporous SNPs (MCM-41/SBA-15) by means of scCO2-assisted SFM at several operational pressures, processing times and depressurization conditions. DXMT was loaded into SNPs (applying a scCO2 solvent impregnation/deposition method - SSID) and into PCL/SNPs composites (using the SFM method). The effects of the employed operational and compositional variables on the physicochemical and morphological features as well as in the in vitro release profiles of DXMT were analyzed in detail. This work demonstrates that the above-referred scCO2-based methods can be very useful for the preparation of DXMT-loaded PCL/SNPs composites with tunable physicochemical, thermomechanical, morphological and drug release properties and suitable for hard-tissue regeneration applications.

Development of natural-based wound dressings impregnated with bioactive compounds and using supercritical carbon dioxide.

Film- and foam-like structures of N-carboxybutylchitosan (CBC) and of agarose (AGA) were prepared and characterized in order to evaluate their potential application as topical membrane-type wound dressing materials, mostly regarding their sustained release capacities and fluid handling properties. Polymeric biomaterials were loaded with two natural-origin bioactive compounds (quercetin and thymol, which present anti-inflammatory and anaesthetic properties, respectively), separately or as a mixture of these two substances, and using a supercritical solvent impregnation (SSI) method. Impregnation experiments were carried out with supercritical carbon dioxide (scCO2) at 10 and 20 MPa, and at 303 and 323 K. Ethanol (10%, v/v) was employed as a co-solvent whenever quercetin was used. Release kinetic studies were performed for all prepared systems and the obtained results showed that higher amounts of quercetin and/or thymol were loaded when higher pressures and temperatures were employed. Results showed that the separated and the simultaneous SSI loading of these two bioactive substances into CBC and AGA is a feasible and advantageous process and that the relative loaded amounts of these substances can be "tuned" simply by changing the operational pressure-temperature conditions. Quercetin presented more sustained release profiles which can be justified by its higher molecular volume and by its lower water solubility as well as by the specific favourable interactions that can be established between quercetin and CBC. Obtained results showed that the employed SSI process also promoted the size reduction of loaded quercetin particles which can significantly improve the solubility of this compound in aqueous solutions. In addition, prepared systems presented adequate water sorption and water vapor sorption capacities as well as water vapor transmission rates that were in the typical and desired ranges for commercial wound dressings.