Search

Submitted by António Freitas (amsf@uma.pt) on 2022-02-10T09:23:59Z No. of bitstreams: 1 Agro-industrial byproducts as modification enhancers of the bacterial cellulose biofilm surface properties.pdf: 2911202 bytes, checksum: 6f56a94be9ebe891641dc8506eb0367c (MD5) Made available in DSpace on 2022-02-10T09:24:00Z (GMT). No. of bitstreams: 1 Agro-industrial byproducts as modification enhancers of the bacterial cellulose biofilm surface properties.pdf: 2911202 bytes, checksum: 6f56a94be9ebe891641dc8506eb0367c (MD5) Previous issue date: 2022 info:eu-repo/semantics/publishedVersion

Nanocomposites composed of poly(glycidyl methacrylate) (PGMA) and bacterial cellulose (BC) were prepared by the in-situ free radical polymerization of glycidyl methacrylate (GMA) inside the BC network. The resulting nanocomposites were characterized in terms of structure, morphology, water-uptake capacity, thermal stability and viscoelastic properties. The three-dimensional structure of BC endowed the nanocomposites with good thermal stability (up to 270 °C) and viscoelastic properties (minimum storage modulus = 80 MPa at 200 °C). In addition, the water-uptake and crystallinity decreased with the increasing content of the hydrophobic and amorphous PGMA matrix. These nanocomposites were then submitted to post-modification via acid-catalysed hydrolysis to convert the hydrophobic PGMA into the hydrophilic poly(glyceryl methacrylate) (PGOHMA) counterpart, which increased the hydrophilicity of the nanocomposites and consequently improved their water-uptake capacity. Besides, the post-modified nanocomposites maintained a good thermal stability (up to 250 °C), viscoelastic properties (minimum storage modulus = 171 MPa at 200 °C) and porous structure. In view of these results, the PGMA/BC nanocomposites can be used as functional hydrophobic nanocomposites for post-modification reactions, whereas the PGOHMA/BC nanocomposites might have potential for biomedical applications requiring hydrophilic, swellable and biocompatible materials. published

To develop bio-nanocomposites using natural biopolymers, nanocomposite films were prepared based on sodium alginate and kapok nanofibrils (CNFs). CNFs when subjected to TEMPO-mediated oxidation gave rise to cellulose nanocrystals (TOCNCs), with carboxyl groups at the surface (Ka/Kb = 3.64). The differences between the two types of nanocelluloses (nanofibrils and nanocrystals) and their impact in the preparation of bio-nanocomposites, were studied. When incorporated in the matrix, the CNFs particles have the tendency to form surface aggregation (Ka/Kb = 2.37), distorting the alginate network, creating heterogeneous films, with high surface roughness (Sa = 29.37 nm), porosity (Dp = 0.087 cm2/min) and vulnerability to heat. The TOCNCs present good dispersion creating a 3D network, which forms uniform (Dp = 0.122 cm2/min) and homogeneous films, with smooth surface (Sa = 16.83 nm). The ultrasonication treatment facilitated the dispersion improving the interfacial interaction between the reinforcing phase and the matrix. The results show the reinforcement potential of kapok nanocellulose in an industrially and medically important biopolymer, sodium alginate, especially when TOCNCs and ultrasonication were used., Materials science; Nanotechnology; Nanomaterials; Materials characterization; Materials property; Agricultural technology; Nanofibrils; Nanocrystals; TEMPO-Mediated oxidation; Sodium alginate; Kapok fiber; Nanocomposite

The increasing water pollution caused by the presence of nano- and microplastics has shown a need to pursue solutions to remediate this problem. In this work, an extracellular polymeric substance (EPS) producing freshwater Cyanothece sp. strain was exposed to nano- and microplastics. The bioflocculant capacity of the biopolymer produced was evaluated. The influence of different concentrations (1 and 10 mg L−1) of polystyrene nano- and microplastics in the extracellular carbohydrates and in the EPS production was studied. The presence of nano- and microplastics induced a negative effect on the microalgal growth (of up to 47%). The results show that the EPS produced by Cyanothece sp. exhibits high bioflocculant activity in low concentrations. Also, the EPS displayed very favourable characteristics for aggregation, as the aggregates were confirmed to consist of microalga, EPS and both the nano- and microplastics. These results highlight the potential of the microalgal-based biopolymers to replace hazardous synthetic flocculants used in wastewater treatment, while aggregating and flocculating nano- and microplastics, demonstrating to be a multi-purposed, compelling, biocompatible solution to nano- and microplastic pollution.

Microplastics (MPs) are widely spread throughout aquatic systems and water bodies. Given that water quality is one of the most important parameters in the microalgal-based industry, it is critical to assess the biochemical impact of short- and long-term exposure to MPs pollution. Here, the microalga Phaeodactylum tricornutum was exposed to water contaminated with 0.5 and 50 mg L-1 of polystyrene (PS) and/or polymethyl methacrylate (PMMA). Results show that the microalgal cultures exposed to lower concentrations of PS displayed a growth enhancement of up to 73% in the first stage (days 3-9) of the exponential growth phase. Surprisingly, and despite the fact that long-term exposure to MPs contamination did not impair microalgal growth, a steep decrease in biomass production (of up to 82%) was observed. The production of photosynthetic pigments was shown to be pH-correlated during the full growth cycle, but cell density-independent in later stages of culturing. The extracellular carbohydrates production exhibited a major decrease during long-term exposure. Still, the production of extracellular proteins was not affected by the presence of MPs. This pilot laboratory-scale study shows that the microalgal exposure to water contaminated with MPs disturbs its biochemical equilibrium in a time-dependent manner, decreasing biomass production. Thus, microalgal industry-related consequences derived from the use of MPs-contaminated water are a plausible possibility.

Microalgae can excrete exopolymer substances (EPS) with a potential to form hetero-aggregates with microplastic particles. In this work, two freshwater (Microcystis panniformis and Scenedesmus sp.) and two marine (Tetraselmis sp. and Gloeocapsa sp.) EPS producing microalgae were exposed to different microplastics. In this study, the influence of the microplastic particles type, size and density in the production of EPS and hetero-aggregates potential was studied. Most microalgae contaminated with microplastics displayed a cell abundance decrease (of up to 42%) in the cultures. The results showed that the formed aggregates were composed of microalgae and EPS (homo-aggregates) or a combination of microalgae, EPS and microplastics (hetero-aggregates). The hetero-aggregation was dependent on the size and yield production of EPS, which was species specific. Microcystis panniformis and Scenedesmus sp. exhibited small EPS, with a higher propension to disaggregate, and consequently lower capabilities to aggregate microplastics. Tetraselmis sp. displayed a higher ability to aggregate both low and high-density microplastics, being partially limited by the size of the microplastics. Gloeocapsa sp. had an outstanding EPS production and presented excellent microplastic aggregation capabilities (adhered onto the surface and also incorporated into the EPS). The results highlight the potential of microalgae to produce EPS and flocculate microplastics, contributing to their vertical transport and consequent deposition. Thus, this work shows the potential of microalgae as biocompatible solutions to water microplastics treatment. published

Phthalate esters are highly present in aquatic plastic litter, which can interfere with the biological processes in the wildlife. In this work, the commonly found freshwater microalga Scenedesmus sp. was exposed to environmental concentrations (0.02, 1 and 100 μg L−1) and to a higher concentration (500 μg L−1) of dibutyl phthalate (DBP), which is an environmental pollutant. The growth, pH variation, production of photosynthetic pigments, proteins and carbohydrates were evaluated. The main inhibition effect of DBP on the microalgal growth was observed in the first 48 h of the exposure (EC50: 41.88 μg L-1). A reduction in the photosynthetic pigment concentration was observed for the 0.02, 1 and 100 μg L-1 conditions indicating that the DBP downregulated the growth rate and affected the photosynthetic process. A significant increase in protein production was only observed under 500 μg L−1 DBP exposure. The extracellular carbohydrates production slightly decreased with the presence of DBP, with a stronger decrease occurring in the 500 μg L-1 condition. These results highlight the environmental risk evaluation and ecotoxicological effects of DBP on the production of biovaluable compounds by microalgae. The results also emphasize the importance of assessing the consequences of the environmental concentrations exposure as a result of the DBP dose-dependent correlation effects.

Bacterial cellulose (BC) has recently been the subject of a considerable amount of research, not only for its environmentally friendly biosynthesis, but also for its high potential in areas such as biomedicine or biomaterials. A symbiotic relationship between a photosynthetic microalga, Chlamydomonas debaryana, and a cellulose producer bacterium, Komagataeibacter saccharivorans, was established in order to obtain a viable and active biofilm. The effect of the growth media composition ratio on the produced living material was investigated, as well as the microalgae biomass quantity, temperature, and incubation time. The optimal temperature for higher symbiotic biofilm production was 30 &deg, C with an incubation period of 14 days. The high microalgae presence, 0.75% w/v, and 60:40 HS:BG-11 medium (v/v) induced a biofilm microalgae incorporation rate of 85%. The obtained results report, for the first time, a successful symbiotic interaction developed in situ between an alkaline photosynthetic microalga and an acetic acid bacterium. These results are promising and open a new window to BC living biofilm applications in medical fields that have not yet been explored.

Made available in DSpace on 2018-12-11T16:54:59Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-09-01 University Grants Commission Fabricating novel materials for biomedical applications mostly require the use of biodegradable materials. In this work biodegradable materials like polylactic acid (PLA) and chitosan (CHS) were used for designing electrospun mats. This work reports the physical and chemical characterization of the PLA–CHS composite, prepared by the electrospinning technique using a mixed solvent system. The addition of chitosan into PLA, offered decrease in fiber diameter in the composites with uniformity in the distribution of fibers with an optimum at 0.4wt% CHS. The fiber formation and the reduction in fiber diameter were confirmed by the SEM micrograph. The inverse gas chromatography and contact angle measurements supported the increase of hydrophobicity of the composite membrane with increase of filler concentration. The weak interaction between PLA and chitosan was confirmed by Fourier transform infrared spectroscopy and thermal analysis. The stability of the composite was established by zeta potential measurements. Cytotoxicity studies of the membranes were also carried out and found that up to 0.6% CHS the composite material was noncytotoxic. The current findings are very important for the design and development of new materials based on polylactic acid-chitosan composites for environmental and biomedical applications. [Figure not available: see fulltext.]. International and Interuniversity Centre for Nanoscience and Nanotechnology Mahatma Gandhi University, Priyadarsini Hills P.O. Department of Chemistry Mar Thoma College, Kuttapuzha P.O. Department of Chemistry C.M.S. College Food and Bioproduct Sciences University of Saskatchewan Faculty of Exact Science and Engineering University of Madeira CIIMAR University of Porto Institute of Chemistry-UNESP, CP 355, Zip 14801-970 Institute of Chemistry-UNESP, CP 355, Zip 14801-970

A novel method to synthesize highly crosslinked bacterial cellulose (BC) is reported. The glyoxalization is started in-situ, in the culture medium during biosynthesis of cellulose by Gluconacetobacter medellensis bacteria. Strong crosslinked networks were formed in the contact areas between extruded cellulose ribbons by reaction with the glyoxal precursors. The crystalline structure of cellulose was preserved while the acidic component of the surface energy was reduced. As a consequence, its predominant acidic character and the relative contribution of the dispersive component increased, endowing the BC network with a higher hydrophobicity. This route for in-situ crosslinking is expected to facilitate other modifications upon biosynthesis of cellulose ribbons by microorganisms and to engineer the strength and surface energy of their networks.

Inverse gas chromatography (IGC) is a technique for evaluating surface properties. The current work emphasizes the use of IGC to evaluate the surface physicochemical changes during different bacterial cellulose (BC) processing methods as well as upon polyaniline (PANi) incorporation. The processing methods (oven-drying, freeze-drying, and regeneration) caused changes in the BC surface group distribution, where upon freeze-drying and regeneration, a more acidic behavior is obtained, compared to oven-drying (Kb/Ka decreased up to 24%). Through freeze-drying, the structural pore preservation increases (54%) the BC porosity, whereas through regeneration, the porosity decreases (23%), compared to BC oven-drying. Regarding the nanocomposites, with PANi incorporation, the overall properties evaluated by IGC were significantly changed. The $$\gamma_{\text{s}}^{\text{total}}$$ increases up to 150%, indicating a more reactive surface in the nanocomposites. Also, is observed a sevenfold increase in the Kb/Ka and a less porous surface (up to 85%). Hence, the current work highlights the use of IGC as a viable technique to evaluate the physicochemical changes upon different BC modifications.

Bacterial cellulose/polyaniline (BC/PANi) blends present a great potential for several applications. The current study evaluates the impact of using different BC matrixes (drained, freeze-dried and regenerated) and different synthesis conditions (in situ and ex situ) to improve the inherent properties of BC, which were monitored through FTIR-ATR, EDX, XRD, SEM, AFM, swelling, contact angle measurement and IGC. The employment of in situ polymerization onto drained BC presented the most conductive membrane (1.4 × 10−1 S/cm). The crystallinity, swelling capacity, surface energy and acid/base behavior of the BC membranes is substantially modified upon PANi incorporation, being dependent on the BC matrix used, being the freeze-dried BC blends the ones with highest crystallinity (up to 54%), swelling capacity (up to 414%) and surface energy (up to 75.0 mJ/m2). Hence, this work evidenced that the final properties of the BC/PANi blends are greatly influenced by both the BC matrixes and synthesis methods employed.

Submitted by António Freitas (amsf@uma.pt) on 2021-04-15T20:40:03Z No. of bitstreams: 1 Polylactic acid nano chitosan composite fibers and their morphological, physical characterization for the removal of cadmium.pdf: 5096005 bytes, checksum: 7c5c2155f86a01e74f93df42c793eefe (MD5) Made available in DSpace on 2021-04-15T20:40:03Z (GMT). No. of bitstreams: 1 Polylactic acid nano chitosan composite fibers and their morphological, physical characterization for the removal of cadmium.pdf: 5096005 bytes, checksum: 7c5c2155f86a01e74f93df42c793eefe (MD5) Previous issue date: 2020 info:eu-repo/semantics/publishedVersion

The use of non-wood fibers in the paper industry has been an economical and environmental necessity. The application of dry-strength agents has been a successful method to enhance the strength properties of paper. The experimental results evidencing the potential of chitosan and cationic starch utilization in bagasse paper subjected to hot water pre-extraction has been presented in this paper. The research analyzes the surface properties alterations due to these dry-strength agents. Inverse gas chromatography was used to evaluate the properties of surface chemistry of the papers namely the surface energy, active sites, surface area as well as the acidic/basic character. The results of the study revealed that the handsheets process causes surface arrangement and orientation of chemical groups, which induce a more hydrophobic and basic surface. The acid-base surface characteristics after the addition of dry-strength agents were the same as the bagasse handsheets with and without hot water pre-extraction. The results showed that the dry-strength agent acts as a protecting film or glaze on the surfaces of bagasse paper handsheets.

In this work, a simple and green route to the synthesis of the bacterial nanocellulose-calcium carbonate (BNC/CaCO3) hybrid bionanocomposites using one-step in situ biosynthesis was studied. The CaCO3 was incorporated in the bacterial nanocellulose structure during the cellulose biosynthesis by Gluconacetobacter xylinus PTCC 1734 bacteria. Hestrin-Schramm (HS) and Zhou (Z) culture media were used to the hybrid bionanocomposites production and the effect of ethanol addition was investigated. Attenuated total reflection Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, inverse gas chromatography and thermogravimetric analysis were used to characterize the samples. The experimental results demonstrated that the ethanol and culture medium play an important role in the BNC/CaCO3 hybrid bionanocomposites production, structure and properties. The BNC/CaCO3 biosynthesized in Z culture medium revealed higher O/C ratio and amphoteric surface character, which justify the highest CaCO3 content incorporation. The CaCO3 was incorporated into the cellulosic matrix decreasing the bacterial nanocellulose crystallinity. This work reveals the high potential of in situ biosynthesis of BNC/CaCO3 hybrid bionanocomposites and opens a new way to the high value-added applications of bacterial nanocellulose.

Biodegradable nanocomposite films were prepared by incorporation of cellulose nanofibrils (CNF) into alginate biopolymer using the solution casting method. The effects of CNF content (2.5, 5, 7.5, 10 and 15 wt %) on mechanical, biodegradability and swelling behavior of the nanocomposite films were determined. The results showed that the tensile modulus value of the nanocomposite films increased from 308 to 1403 MPa with increasing CNF content from 0% to 10%; however, it decreased with further increase of the filler content. Incorporation of CNF also significantly reduced the swelling percentage and water solubility of alginate-based films, with the lower values found for 10 wt % in CNF. Biodegradation studies of the films in soil confirmed that the biodegradation time of alginate/CNF films greatly depends on the CNF content. The results evidence that the stronger intermolecular interaction and molecular compatibility between alginate and CNF components was at 10 wt % in CNF alginate films.

Nanocellulose was successfully extracted from five different lignocellulosic biomass sources viz. banana rachis, sisal, kapok, pineapple leaf and coir using a combination of chemical treatments such as alkaline treatment, bleaching and acid hydrolysis. The shape, size and surface properties of the nanocellulose generally depend on the source and hydrolysis conditions. A comparative study of the fundamental properties of raw material, bleached and nanocellulose was carried out by means of Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, birefringence, X-ray diffraction, inverse gas chromatography and thermogravimetric analysis. Through the characterization of the nanocellulose obtained from different sources, the isolated nanocellulose showed an average diameter in the range of 10–25 nm, high crystallinity, high thermal stability and a great potential to be used with acid coupling agents due to a predominantly basic surface. This work provides an insight into the effective utilization of a variety of plant biomass as a potential source for nanocellulose extraction.

The lipophilic extracts from the storage root of 13 cultivars of sweet potato (Ipomoea batatas (L.) Lam.) were evaluated by gas chromatography-mass spectrometry with the aim to valorize them and offer information on their nutritional properties and potential health benefits. The amount of lipophilic extractives ranged from 0.87 to 1.32% dry weight. Fatty acids and sterols were the major families of compounds identified. The most abundant saturated and unsaturated fatty acids were hexadecanoic acid (182-428 mg/kg) and octadeca-9,12-dienoic acid (133-554 mg/kg), respectively. β-Sitosterol was the principal phytosterol, representing 55.2-77.6% of this family, followed by campesterol. Long-chain aliphatic alcohols and α-tocopherol were also detected but in smaller amounts. The results suggest that sweet potato should be considered as an important dietary source of lipophilic phytochemicals.

In this work, the effects of hot water pre-extraction of depithed bagasse on the soda pulping and surface properties were studied. The conditions of hot water pre-extraction were: maximum temperature 170 °C, heat-up time 90 min, time at maximum temperature 10 min, and solid to liquor ratio (S:L) 1:8. Consequently, the pre-extracted and un-extracted bagasse chips were subjected to soda pulping at 160 °C for 1 h with 11, 14 and 17% active alkali charge and an S:L of 1:5. The results showed that the hot water pre-extraction increased bagasse surface texture porosity by hemicellulose degradation. Therefore, the delignification was faster for pulping of pre-extracted samples. At a certain charge of alkali, pre-extracted samples showed higher screened yield and lower Kappa number. For instance, at 17% alkali charge, pre-extracted bagasse gave 11.3% higher pulp yield compared with the un-extracted ones. Inverse gas chromatography (IGC) results showed that the hot water pre-extraction changed the active sites on the bagasse surface, decreasing the dispersive energy and the basicity character, and affected the particle morphology. The pulping process decreased the hydrophobicity and the basicity of the bagasse surface. The surfaces of un-extracted and pre-extracted bagasse pulps had similar properties but different morphology. The pulps present higher surface area and permeability with more reactive capacity.

The effect of saponin on the surface properties of banana fibres was studied by Inverse Gas Chromatography (IGC). Parameters including the dispersive component of the surface energy, surface heterogeneity, surface area, as well as acid–base surface properties were determined for saponin modified banana micro and nanofibres. These parameters show a more extensive saponin coating on the nanofibres with a network formation which is explained by the higher reactivity of nanofibres due to the higher surface energy, specific interaction and higher surface area presented by the nanofibres. The energetic profile indicates that both micro and nanofibres coated with saponin interact with the same, or similar, energy active sites. Saponin treatment reduces considerably the surface area of the fibres, with the consequent decrease in the monolayer capacity. The interaction with the polar probes clearly indicates that saponin treatment creates new polar active sites for specific interactions in both samples. However, the treatment increases predominately the basicity of the fibre surface with more relevance to the nanofibres. This behaviour will lead to better polymer/fibre interaction during composite preparation.