Fast and sustainable production of smart nanofiber mats by solution blow spinning for food quality monitoring: Potential of polycaprolactone and agri-food residue-derived anthocyanins.

The shelf life of perishable foods is estimated through expensive and imprecise analyses that do not account for improper storage. Smart packaging, obtained by agile manufacturing of nanofibers functionalized with natural pigments from agri-food residues, presents promising potential for real-time food quality monitoring. This study employed the solution blow spinning (SBS) technique for the rapid production of smart nanofiber mats based on polycaprolactone (PCL), incorporating extracts of agricultural residues rich in anthocyanins from eggplant (EE) or purple cabbage (CE) for monitoring food quality. The addition of EE or CE to the PCL matrix increased the viscosity of the solution and the diameter of the nanofibers from 156 nm to 261-370 nm. The addition of extracts also improved the mechanical and water-related properties of the nanofibers, although it reduced the thermal stability. Attenuated total reflectance Fourier-transform infrared spectroscopy confirmed the incorporation of anthocyanins into PCL nanofibers. Nanofiber mats incorporated with EE or CE exhibited visible color changes (ΔE ≥ 3) in response to buffer solutions (pH between 3 and 10), and ammonia vapor. Smart nanofibers have demonstrated the ability to monitor fish fillet spoilage through visible color changes (ΔE ≥ 3) during storage. Consequently, smart nanofibers produced by the SBS technique, using PCL and anthocyanins from agro-industrial waste, reveal potential as smart packaging materials for food.

Multidimensional calibration spaces in Staphylococcus Aureus detection using chitosan-based genosensors and electronic tongue.

Mastitis diagnosis can be made by detecting Staphylococcus aureus (S. aureus), which requires high sensitivity and selectivity. Here, we report on microfluidic genosensors and electronic tongues to detect S. aureus DNA using impedance spectroscopy with data analysis employing visual analytics and machine learning techniques. The genosensors were made with layer-by-layer films containing either 10 bilayers of chitosan/chondroitin sulfate or 8 bilayers of chitosan/sericin functionalized with an active layer of cpDNA S. aureus. The specific interactions leading to hybridization in these genosensors allowed for a low limit of detection of 5.90 × 10-19 mol/L. The electronic tongue had four sensing units made with 6-bilayer chitosan/chondroitin sulfate films, 10-bilayer chitosan/chondroitin sulfate, 8-bilayer chitosan/sericin, and 8-bilayer chitosan/gold nanoparticles modified with sericin. Despite the absence of specific interactions, various concentrations of DNA S. aureus could be distinguished when the impedance data were plotted using a dimensionality reduction technique. Selectivity of S. aureus DNA was confirmed using multidimensional calibration spaces, based on machine learning, with accuracy up to 89 % for the genosensors and 66 % for the electronic tongue. Hence, with these computational methods one may opt for the more expensive genosensors or the simpler and cheaper electronic tongue, depending on the sensitivity level required to diagnose mastitis.

Membranes composed of poly(lactic acid)/poly(ethylene glycol) and Ora-pro-nóbis (Pereskia aculeata Miller) extract for dressing applications.

Wounds are considered one of the most critical medical conditions that must be managed appropriately due to the psychological and physical stress they cause for patients, as well as creating a substantial financial burden on patients and global healthcare systems. Nowadays, there is a growing interest in developing nanofiber mats loaded with varying plant extracts to meet the urgent need for advanced wound ressings. This study investigated the development and characterization of poly(lactic acid) (PLA)/ poly(ethylene glycol) (PEG) nanofiber membranes incorporated with Ora-pro-nóbis (OPN; 12.5, 25, and 50 % w/w) by the solution-blow-spinning (SBS) technique. The PLA/PEG and PLA/PEG/OPN nanofiber membranes were characterized by scanning electron microscopy (SEM), thermal properties (TGA and DSC), Fourier transform infrared spectroscopy (FTIR), contact angle measurements and water vapor permeability (WVTR). In addition, the mats were analyzed for swelling properties in vitro cell viability, and fibroblast adhesion (L-929) tests. SEM images showed that smooth and continuous PLA/PEG and PLA/PEG/OPN nanofibers were obtained with a diameter distribution ranging from 171 to 1533 nm. The PLA/PEG and PLA/PEG/OPN nanofiber membranes showed moderate hydrophobicity (~109-120°), possibly preventing secondary injuries during dressing removal. Besides that, PLA/PEG/OPN nanofibers exhibited adequate WVTR, meeting wound healing requirements. Notably, the presence of OPN gave the PLA/PEG membranes better mechanical properties, increasing their tensile strength (TS) from 3.4 MPa (PLA/PEG) to 5.3 MPa (PLA/PEG/OPN), as well as excellent antioxidant properties (Antioxidant activity with approximately 45 % oxidation inhibition). Therefore, the nanofiber mats based on PLA/PEG, especially those incorporated with OPN, are promising options for use as antioxidant dressings to aid skin healing.

Employing alternative culture media in kefiran exopolysaccharide production: Impact on microbial diversity, physicochemical properties, and bioactivities.

Kefiran is a biomaterial with potential application in developing novel materials for food technology. In this study, sugarcane sugar (REF), raw sugar (RAS), brown sugar (BRS), soy molasses (SOM), and sugarcane molasses (SCM) were evaluated for the production of kefiran from kefir biomass rather than cow's milk (CMK), the usual medium. The produced kefiran was purified and characterized by colorimetry, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis, and morphology. It was also assayed for antioxidant and antimicrobial activity. SCM had the highest average daily rate of kefir biomass production (29.17 %/day). The composition of the culture medium affected the microbial diversity of kefir grains, and the Lactobacillus genus was the most abundant (39.8 %, 40.0 %, and 83.9 % to SCM, SOM, and CMK, respectively) in the samples that presented the highest biomass production and kefiran extraction yields. FTIR spectra showed that the bands of kefiran produced in REF and RAS were narrower than those of the other samples. Kefiran grew in an alternative culture medium also exhibited higher thermal stability (Tonset and TMax was higher than 250 and 280 °C, respectively). Those grown in SOM and SCM displayed antimicrobial and antioxidant activities similar to those of kefiran produced in CMK. The results indicate that agro-industrial by-products (SCM and SOM) are potential alternatives for kefiran production from kefir biomass.

Nanoarchitectonic E-Tongue of Electrospun Zein/Curcumin Carbon Dots for Detecting Staphylococcus aureusin Milk.

We report a nanoarchitectonic electronic tongue made with flexible electrodes coated with curcumin carbon dots and zein electrospun nanofibers, which could detect Staphylococcus aureus(S. aureus) in milk using electrical impedance spectroscopy. Electronic tongues are based on the global selectivity concept in which the electrical responses of distinct sensing units are combined to provide a unique pattern, which in this case allowed the detection of S. aureus through non-specific interactions. The electronic tongue used here comprised 3 sensors with electrodes coated with zein nanofibers, carbon dots, and carbon dots with zein nanofibers. The capacitance data obtained with the three sensors were processed with a multidimensional projection technique referred to as interactive document mapping (IDMAP) and analyzed using the machine learning-based concept of multidimensional calibration space (MCS). The concentration of S. aureus could be determined with the sensing units, especially with the one containing zein as the limit of detection was 0.83 CFU/mL (CFU stands for colony-forming unit). This high sensitivity is attributed to molecular-level interactions between the protein zein and C-H groups in S. aureus according to polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) data. Using machine learning and IDMAP, we demonstrated the selectivity of the electronic tongue in distinguishing milk samples from mastitis-infected cows from milk collected from healthy cows, and from milk spiked with possible interferents. Calibration of the electronic tongue can also be reached with the MCS concept employing decision tree algorithms, with an 80.1% accuracy in the diagnosis of mastitis. The low-cost electronic tongue presented here may be exploited in diagnosing mastitis at early stages, with tests performed in the farms without requiring specialized laboratories or personnel.

Obtaining poly (lactic acid) nanofibers encapsulated with peppermint essential oil as potential packaging via solution-blow-spinning.

The development of active packaging based on biodegradable material and incorporating active compounds, such as essential oil, is a new technique to ensure food safety without harming the environment. In this study, nanofiber mats of poly (lactic acid)/ polyethylene glycol (PLA/PEG) blend incorporated with peppermint essential oil (PO) at different ratios (5-20 % v/w) were produced by solution-blow-spinning (SBS) for potential packaging application. Electron microscopy showed a cylindrical and interlaced morphology for PLA/PEG/PO and a significant increase in the diameter (139-192 nm) of the nanofibers by increasing PO content. All nanofibers showed high thermal stability (278-345 °C) suitable for use in the food industry. Nuclear magnetic resonance (13C NMR) spectrum confirmed PO in the nanofibers after SBS. ATR-FTIR spectral analysis supported the chemical composition of the nanofiber mats. PO addition led to obtaining hydrophobic nanofibers, enhancing the contact angle to 122° and decreasing water vapor permeability (60 % reduction compared to the PLA/PEG (3.0 g.mm.kPa-1.h-1.m-2). Although the PLA/PEG/20%PO nanofibers did not show halo formation in 24 h, they effectively extended the strawberries' shelf-life at 25 °C, evidencing PO release over time. It also reduced weight loss (2.5 % and 0.3 % weight loss after 5 days for PLA/PEG and PLA/PEG/20%PO, respectively) and increased firmness (8-12 N) for strawberries packed with the nanofiber mats. It is suggested that PLA/PEG films incorporating PO may be used as an active, environmentally friendly packaging material.

Pectin-based color indicator films incorporated with spray-dried Hibiscus extract microparticles.

Colorimetric films incorporated with anthocyanins as an indicator for freshness monitoring have aroused growing interest recently. The pH-sensing colorimetric film were developed based on pectin (HM), containing aqueous hibiscus extract microparticles (HAE). HAE microparticles were obtained by spray drying with different wall materials (Inulin -IN, maltodextrin- MD and their combination). The films were obtained on large scale by continuous casting. These films were characterized for physicochemical analysis, morphological structure, thermal and barrier properties, antioxidant activity, and color change at different pH. The addition of HAE microparticles caused relevant changes to HM-based films, such as in mechanical behavior and improved barrier property (11-22% WVTR reduction) depending on the type of wall material used and the concentration added. It was verified with the thermal stability of films, with a slight increase being observed. The color variation of smart films was entirely pH-dependent. Overall, the proposed color indicator films showed unique features and functionalities and could be used as an alternative natural pH indicator in smart packaging systems.

Development of alginate/pectin microcapsules by a dual process combining emulsification and ultrasonic gelation for encapsulation and controlled release of anthocyanins from grapes (Vitis labrusca L.).

The aim of this study was to investigate the physicochemical, morphological, and gastrointestinal release properties of an anthocyanin-rich extract of grapes in alginate and pectin beads as carriers; the effects of ultrasonic gelation combined with emulsification were also investigated. In general, the alginate beads showed smaller size and more regular shape compared to pectin. The effect of emulsification combined with ionic gelation was more pronounced in the alginate beads and resulted in higher retention of anthocyanins, higher antioxidant capacity, and also allowed the best release profile during intestinal digestion. Thus, the simultaneous strategy could be an interesting delivery system and enhance the release of anthocyanins, providing an opportunity for the development of ingredients with different bioactive properties.

Biodegradability and nutrients release of thermoplastic starch and poly (ε-caprolactone) blends for agricultural uses.

Driven by the environmental stress caused by plastics, the interest on eco-friendly polymers has attracted the attention of researchers and industry. Thermoplastic starch (TPS) and poly (ε-caprolactone) (PCL) blends are good examples of sustainable material, exhibiting synergism between economic viability and properties. However, its biodegradability aligned to nutrients release has been less explored in agricultural applications. Herein, it is proposed the investigation of biodegradability of urea plasticized TPS and PCL blends, compatibilized with PCL grafted with maleic anhydride (PCL-g-MA), aiming fertilizers and sustainable agricultural products. The blends were prepared in a twin-screw extruder using a flat film die. The mechanical, thermal, morphological, and physical properties of TPS-PCL films were characterized, including biodegradation analysis via Bartha respirometer and nitrogen release in the soil. The films presented biodegradability and nitrogen release as a function of TPS content on blends formulation, presenting flexibility and robust mechanical properties. These findings may open a way of multifunctional agricultural products applied as fertilizer materials through economical and sustainable mulching films.

Development of quaternary nanocomposites made up of cassava starch, cocoa butter, lemongrass essential oil nanoemulsion, and brewery spent grain fibers.

We report on production of novel quaternary nanocomposite films based on thermoplastic starch (TPS, 8% w/v) derived from cassava, cocoa butter, (CB, 30% wt.%), and lemongrass essential oil (LEO, 1:1) nanoemulsions reinforced with different concentrations of brewery spent grain (BSG, 5 or 10 wt.%) fibers, by continuous casting. The chemical composition, the morphological, thermal, mechanical properties, film barrier, biodegradability in the vegetable compound, in addition to the application in chocolates, have been widely studied. The addition of CB, LEO, and BSG caused relevant changes in the starch-based films, such as increased extensibility (from 2.4-BSG5 to 9.4%-BSG10) and improved barrier to moisture (2.9 and 2.4 g.mm.kPa-1 .h-1 .m-2 ). Contrastingly, the thermal stability of the starch film was slightly decreased. The biodegradability of the herein developed quaternary nanocomposite films was the same as that of TPS films, eliminating concerns on the supplementation with active ingredients that are expected to have some biocidal effect. Despite checking antimicrobial activity only by contact under the biocomposites, chocolates packed with the films were well accepted by consumers, especially the samples of white chocolate stored in the BSG5 biocomposite. Overall, this new approach towards quaternary active, biodegradable films produced in a pilot-scale lamination unit was successful in either improving or at least maintaining the essential properties of TPS-based films for food packaging applications, while providing them with unique features and functionalities. PRACTICAL APPLICATION: This contribution relates to new approach toward quaternary films produced in a pilot-scale lamination unit. It relates to sustainability as it is both biodegradable and based on plant biomass, as well as produced via a clean, through high-yield process. The four components of the edible films we developed provide it with good in properties performance, as both a passive barrier (i.e. purely physical), and active, related to the sensory attributes of food, essential to be applied in food packaging. The valorization of a BSG also adds to the relevance of our contribution within the circular bioeconomy framework.

Immunosensors containing solution blow spun fibers of poly(lactic acid) to detect p53 biomarker.

This paper reports on biosensors made with a matrix of polylactic acid (PLA) fibers, which are suitable for immobilization of the anti-p53 active layer for detection of p53 biomarker. The PLA fibers were produced with solution blow spinning, a method that is advantageous for its simplicity and possibility to tune the fiber properties. For the biosensors, the optimized time to deposit the fibers was 60 s, with which detection of p53 could be achieved with the limit of detection of 11 pg/mL using electrical impedance spectroscopy. This sensitivity is also sufficient to detect the p53 biomarker in patient samples, which was confirmed by distinguishing samples from cell lines with distinct p53 concentrations in a plot where the impedance spectra were visualized with the interactive document mapping (IDMAP) technique. The high sensitivity and selectivity of the biosensors may be attributed to the specific interaction between the active layer and p53 modeled with a Langmuir-Freundlich and Freundlich isotherms and inferred from the analysis of the vibrational bands at 1550, 1650 and 1757 cm-1 using polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). The successful immobilization of the active layer is evidence that the approach based on solution blown spun fibers may be replicated to other types of biosensors.

Cellulose Nanocrystals from Fibers of Macauba (Acrocomia Aculeata) and Gravata (Bromelia Balansae) from Brazilian Pantanal.

Cellulose nanocrystals (CNC) were obtained from macauba and gravata fibers. Macauba (or Bocaiuva) is a palm tree found throughout most of Brazil and Gravata is an abundant kind of bromelia with 1-2m long leaves, found in Brazilian Pantanal and Cerrado. The raw fibers of both fibers were mercerized with NaOH solutions and bleached; they were then submitted to acid hydrolysis using H2SO4 at 45 °C, varying the hydrolysis time from 15 up to 75 min. The fibers were analyzed by X-ray diffraction (XRD), FTIR Spectroscopy, scanning electron microscopy (SEM) and thermal stability by thermogravimetric analysis (TG). XRD patterns did not present changes in the crystal structure of cellulose after mercerization, but it was observed a decrease of hemicellulose and lignin contents, and consequently an increase of cellulose content with the increase of NaOH solution concentration in the mercerization. After acid hydrolysis, the cellulose nanocrystals (CNC) were also analyzed by transmission electron microscopy (TEM) which showed an acicular or rod-like aspect and nanometric dimensions of CNC from both fibers, but the higher values of aspect ratio (L/D) were found on CNC obtained from gravata after 45 min of acid hydrolysis. The mercerization and subsequent bleaching of fibers influenced the crystallinity index and thermal stability of the resulting CNC, but their properties are mainly influenced by the hydrolysis time, i. e., there is an increase in crystallinity and thermal stability up to 45 min of hydrolysis, after this time, both properties decrease, probably due to the cellulose degradation by the sulfuric acid.

Curaua and eucalyptus nanofibers films by continuous casting: Mechanical and thermal properties.

A wide variety of new green materials such as curaua leaf fibers (CLFs) has potential applications in nanotechnology. This study aims to investigate the thermomechanical properties and morphological structure of cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) films obtained by continuous casting. The CNCs were obtained by acid hydrolysis and CNFs by mechanical shearing from bleached CLFs and eucalyptus pulp. The morphology after continuous casting resulted in oriented nanofibers, and as a consequence there was mechanical anisotropy. CNCs films showed the greatest values of tensile strength (36±4MPa) and the more effective fibrillation provided better mechanical strength of eucalyptus CNFs films than curaua CNFs films. Sulfur groups and mechanical shear degradation affected the stability of CNCs and CNFs films, respectively. Thus, the type of nanostructure, the way they interact to each other, the cellulose source and the process interfere significantly on the properties of the films.

Solution blow spun nanocomposites of poly(lactic acid)/cellulose nanocrystals from Eucalyptus kraft pulp.

Cellulose nanocrystals (CNCs) were extracted from Eucalyptus kraft pulp by sulfuric acid hydrolysis, and esterified with maleic anhydride (CNCMA). The incorporation of sulfate ester groups on the cellulose surface resulted in higher stability of the nanoparticles in aqueous suspensions and lower thermal stability. Then, PLA/CNC and PLA/CNCMA nanocomposites were successfully obtained by solution blow spinning (SBS) using dimethyl carbonate (DMC) as solvent. CNC and CNCMA indicated to be acting both as nucleating agents or growth inhibitors of PLA crystal and tends to favor the formation of PLA crystals of higher stability. A fraction of the nanocrystals indicate to be exposed on the surface of the PLA fibers, since the hydrophilicity of the composite films increased significantly. Such composites may have potential application as filtering membranes or adsorbents.

Effect of lubricant on mechanical and rheological properties of compatibilized PP/sawdust composites.

An investigation was performed regarding the effect of compatibilizer and lubricant concentrations on the mechanical and rheological properties of polypropylene/sawdust composites using two-level factorial central composite design. Maleic anhydride grafted PP (PP-g-MA) was used as compatibilizer and the lubricant used was Struktol TPW 113. Composites without these additives were also prepared. Processing was carried out in a co-rotating twin-screw extruder coupled to a Haake rheometer. Mechanical properties were assessed from tensile tests and rheological properties were evaluated by oscillatory measurements and melt flow index (MFI) test. Tensile strength improved with increasing compatibilizer concentration in the composites and reached a maximum value in the absence of lubricant. When both additives were present tensile strength decreased, suggesting a possible interaction between lubricant and compatibilizer, reducing efficiency of the latter. The general trend observed for rheological results was a decrease in complex viscosity, storage modulus and MFI when both additives were present.

Development of poly(lactic acid) nanostructured membranes for the controlled delivery of progesterone to livestock animals.

Solution blow spinning (SBS) is a novel technology feasible to produce nanostructured polymeric membranes loaded with active agents. In the present study, nanofibrous mats of poly(lactic acid) (PLA) loaded with progesterone (P4) were produced by SBS at different P4 concentrations. The spun membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FTIR). The in vitro releasing of P4 was evaluated using high-performance liquid chromatography (HPLC). Interactions between progesterone and PLA were confirmed by rheological measurements of the PLA/P4 solutions and in the spun mats by microscopy (SEM), thermal (DSC) and spectral (FTIR) analyses. SEM micrographs provided evidences of a smooth and homogeneous structure for nanostructured membranes without progesterone crystals on fiber surface. FTIR spectroscopy indicated miscibility and interaction between the ester of PLA and the ketone groups of the P4 in the nanofibers. X-ray analysis indicated that the size of PLA crystallites increased with progesterone content. Finally, by in vitro release experiments it was possible to observe that the progesterone releasing follows nearly first-order kinetics, probably due to the diffusion of hormone into PLA nanofibers.

Poly(lactic acid)/Carbon Nanotube Fibers as Novel Platforms for Glucose Biosensors.

The focus of this paper is the development and investigation of properties of new nanostructured architecture for biosensors applications. Highly porous nanocomposite fibers were developed for use as active materials in biosensors. The nanocomposites comprised poly(lactic acid)(PLA)/multi-walled carbon nanotube (MWCNT) fibers obtained via solution-blow spinning onto indium tin oxide (ITO) electrodes. The electrocatalytic properties of nanocomposite-modified ITO electrodes were investigated toward hydrogen peroxide (H2O2) detection. We investigated the effect of carbon nanotube concentration and the time deposition of fibers on the sensors properties, viz., sensitivity and limit of detection. Cyclic voltammetry experiments revealed that the nanocomposite-modified electrodes displayed enhanced activity in the electrochemical reduction of H2O2, which offers a number of attractive features to be explored in development of an amperometric biosensor. Glucose oxidase (GOD) was further immobilized by drop coating on an optimized ITO electrode covered by poly(lactic acid)/carbon nanotube nanofibrous mats. The optimum biosensor response was linear up to 800 mM of glucose with a sensitivity of 358 nA·mM-1 and a Michaelis-Menten constant (KM) of 4.3 mM. These results demonstrate that the solution blow spun nanocomposite fibers have great potential for application as amperometric biosensors due to their high surface to volume ratio, high porosity and permeability of the substrate. The latter features may significantly enhance the field of glucose biosensors.