The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby ...obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling. With sub-nanometer Pd species, amines drive to the Heck reaction, carbonate drives to the Sonogahira reaction, and phosphate drives to the Suzuki reaction, while for Pt clusters and single atoms, good conversion is only achieved using acetate as a base. This base-controlled orthogonal reactivity with ligand-free catalysts opens new avenues in the design of cross-coupling reactions in organic synthesis.
Curcumin has uses as a food colorant and functional ingredient, these uses being restrained owing to its low solubility in water, which limits its dispersion in food matrices and its ...bioaccessibility. Curcumin–gelatin microparticles produced by electrohydrodynamic atomization were developed to overcome these problems. Microparticles with a size up to 1.2μm in diameter, in which curcumin was in the amorphous state, were obtained. Both curcumin water solubility and bioaccessibility were significantly improved by encapsulation (38.6 and 11.3-fold higher than commercial curcumin, respectively). A gellified fish product was used to evaluate the coloring capacity of microencapsulated curcumin, finding a better dispersion for microencapsulated curcumin than for commercial one. However, curcumin bioaccessibility was similar owing to curcumin solubilization into the protein matrix. In spite of this, a protective effect of curcumin was observed, as the antioxidant activity of the bioaccessible fraction of the gel supplemented with microencapsulated curcumin was higher.
Curcumin is a potential natural food coloring and functional ingredient which impairs an attractive yellowish-orange color to food and possesses a wide range of biological activities. However its use in food is restrained owing to its low solubility in water. Curcumin encapsulation using a soluble polymer is a promising strategy to widen the use of curcumin as an ingredient in the food industry.
•Electrodynamic atomization has been used to obtain gelatin–curcumin microparticles.•Water solubility and bioaccessibility of curcumin were improved after encapsulation.•Encapsulation improved curcumin dispersion into a gellified fish product.•Encapsulation increased antioxidant activity of curcumin.
•Active EVOH films with natural additives: green tea extract and oregano essential oil.•Agents release provides antioxidant and antimicrobial properties to exposed product.•Release kinetics depend on ...the affinity between active agents and food simulants.•Microbial growth inhibition was observed in both liquid media and in vapour phase.
Polymer films with antioxidant and antimicrobial properties were manufactured for the active packaging of food products. Green tea extract (GTE) and oregano essential oil (OEO) were incorporated in an ethylene–vinyl alcohol copolymer (EVOH). Release studies of the main active components of the films into three food simulants, 3% acetic acid, 10% ethanol and 50% ethanol, were conducted at 4°C and 23°C. The total antioxidant activity at equilibrium was measured in the food simulants and the antimicrobial capacity of the films was tested in vitro against Listeria monocytogenes, Escherichia coli and Penicillium expansum. The results suggest that the release kinetics depend on the affinity between the active agents and the food simulants. In general, the fastest diffusion was obtained when films were exposed to 50% ethanol and that effect was concurrent with greater antioxidant efficiencies. The films also showed microbial growth inhibition in liquid media and in vapour phases, demonstrating that the developed films show strong potential for development as active food packaging films.
Chitosan/cyclodextrin films (CS:CD) incorporating carvacrol were obtained by casting, and conditioned at 23°C and 75% relative humidity prior to being immersed in liquid carvacrol until they reached ...sorption equilibrium. In a previous work, the in vitro antimicrobial activity of these films was studied. In this work, active films were used to inhibit microbial growth in packaged chicken breast fillets. Samples of CS:CD films loaded with carvacrol, of different sizes and thus with different quantities of antimicrobial agent, were stuck to the aluminium lid used to seal PP/EVOH/PP cups containing 25g of chicken fillets. These samples were stored for 9days at 4°C. The packages were hermetically sealed and it was confirmed that they provided an infinite barrier to carvacrol. The partition of the antimicrobial agent within the food/packaging system was analysed. The antimicrobial devices rapidly released a large percentage of the agent load, amounts that were gained by the adhesive coating of the lid and especially by the chicken fillets. The latter were the main sorbent phase, with average concentrations ranging between 200 and 5000mg/Kg during the period of storage. The microbiota of the packaged fresh chicken fillets – mesophiles, psychrophiles, Pseudomonas spp., enterobacteria, lactic acid bacteria and yeasts and fungi – were analysed and monitored during storage. A general microbial inhibition was observed, increasing with the size of the active device. Inhibition with a 24cm2 device ranged from 0.3 log reductions against lactic acid bacteria to 1.8logs against yeasts and fungi. However, the large amount of antimicrobial that was sorbed or that reacted with the fillet caused an unacceptable sensory deterioration. These high sorption values are probably due to a great chemical compatibility between chicken proteins and carvacrol.
•Fast release of carvacrol from a chitosan–cyclodextrin device•Antimicrobial effect of carvacrol depends on the headspace concentration.•Great retention of carvacrol by chicken proteins reduces antimicrobial activity.•Sensorial deterioration of product limits the amount of carvacrol to be incorporated.
A chromatic sensor has been designed for the detection of oxygen in package headspace. The sensor is based on the redox change of methylene blue (MB) to its leuco form. Its formulation includes the ...pigment, glycerol, as a sacrificial electron donor, TiO
, as a photocatalyst and ethylene-vinyl alcohol copolymer (EVOH), as a structural polymer matrix. The final sensor design that allows its manufacture by conventional printing and laminating technologies consists of the sensing polymer matrix (MB-EVOH) sandwiched in a suitable transparent multilayer structure. The outer layers protect the sensor from the external atmosphere and allow visualization of the colour. The inner layer is sufficiently opaque to facilitate sensor reading from the outside, is thick enough to avoid direct contact with food (functional barrier), and is oxygen-permeable to expose the sensing material to the internal package atmosphere. In the absence of oxygen, the sensor becomes white by irradiation with halogen lamps in less than 60 s. All components are substances permitted for food contact except the pigment, but specific migration analysis showed no trace of migration thanks to the functional barrier included in the design.
Advancements in polymer science and nanotechnology hold significant potential for addressing the increasing demands of food security, by enhancing the shelf life, barrier properties, and nutritional ...quality of harvested fruits and vegetables. In this context, biopolymer-based delivery systems present themselves as a promising strategy for encapsulating bioactive compounds, improving their absorption, stability, and functionality. This study provides an exploration of the synthesis, characterization, and postharvest protection applications of nanocarriers formed through the complexation of chitosan oligomers, carboxymethylcellulose, and alginate in a 2:2:1 molar ratio. This complexation process was facilitated by methacrylic anhydride and sodium tripolyphosphate as cross-linking agents. Characterization techniques employed include transmission electron microscopy, energy-dispersive X-ray spectroscopy, infrared spectroscopy, thermal analysis, and X-ray powder diffraction. The resulting hollow nanospheres, characterized by a monodisperse distribution and a mean diameter of 114 nm, exhibited efficient encapsulation of carvacrol, with a loading capacity of approximately 20%. Their suitability for phytopathogen control was assessed in vitro against three phytopathogens-
,
, and
-revealing minimum inhibitory concentrations ranging from 23.3 to 31.3 μg·mL
. This indicates a higher activity compared to non-encapsulated conventional fungicides. In ex situ tests for tomato (cv. 'Daniela') protection, higher doses (50-100 μg·mL
, depending on the pathogen) were necessary to achieve high protection. Nevertheless, these doses remained practical for real-world applicability. The advantages of safety, coupled with the potential for a multi-target mode of action, further enhance the appeal of these nanocarriers.
•CO2 and O2 are critical factors for controlling tomato postharvest behaviour.•The influence of MAP was more noticeable in the short life tomato cultivar.•MAP was more effective than reducing ...ethylene for delaying color change and quality loss.•Reducing ethylene concentration increased TP and AA in the short life tomato cultivar.
Controlling storage atmosphere is a key factor for delaying postharvest fruit quality loss. The objective of this study is to evaluate its influence on physico-chemical, sensorial and nutritional quality attributes of two tomato fruit cultivars (Delizia and Pitenza) that respectively have a short- and long-storage life. To that end, the effect of two types of bags with different gas permeability, combined or not with an ethylene sorbent, on tomato organoleptic and nutritional properties were compared during fruit storage at 13°C. CO2 and O2 were critical factors for controlling tomato postharvest behaviour. Weight loss, firmness, color and visual quality were only affected by bag permeability just as total sugar content and acidity for Pitenza tomatoes. (trans)-2-Hexenal also appears to be related with CO2 and O2 levels. Lycopene, total phenols (TP) and ascorbic acid (AA) contents were also affected by the packaging form and the storage length. Ethylene removal in combination with MAP led to a higher content in TP and AA in the short-life tomato cultivar.
Ethylene vinyl alcohol copolymer (EVOH) films containing green tea extract were successfully produced by extrusion. The films were brown and translucent, and the addition of the extract increased the ...water and oxygen barrier at low relative humidity but increased the water sensitivity, the glass transition temperature, and the crystallinity of the films and improved their thermal resistance. An analysis by HPLC revealed that the antioxidant components of the extract suffered partial degradation during extrusion, reducing the content of catechin gallates and increasing the concentration of free gallic acid. Exposure of the films to various food simulants showed that the liquid simulants increased their capacity to reduce DPPH• and ABTS•+ radicals. The release of green tea extract components into the simulant monitored by HPLC showed that all compounds present in the green tea extract were partially released, although the extent and kinetics of release were dependent on the type of food. In aqueous food simulants, gallic acid was the main antioxidant component released with partition coefficient values ca. 200. In 95% ethanol (fatty food simulant) the K value for gallic acid decreased to 8 and there was a substantial contribution of catechins (K in the 1000 range) to a greatly increased antioxidant efficiency. Kinetically, gallic acid was released more quickly than catechins, owing to its faster diffusivity in the polymer matrix as a consequence of its smaller molecular size, although the most relevant effect is the plasticization of the matrix by alcohol, increasing the diffusion coefficient >10-fold. Therefore, the materials here developed with the combination of antioxidant substances that constitute the green tea extract could be used in the design of antioxidant active packaging for all type of foods, from aqueous to fatty products, the compounds responsible for the protection being those with the higher compatibility with the packaged product.
This study aims to develop antimicrobial films consisting of chitosan and silver nanoparticles that are homogeneously distributed throughout the polymer matrix. Nanoparticles were generated in situ ...during the neutralization of the chitosan acetate film with sodium hydroxide. The temperature of neutralization and the concentration of silver in the film were crucial determinants of the shape and size of the nanoparticles. Neutralized films exhibited antimicrobial activity against Escherichia coli and Staphylococcus aureus in liquid growth media. However, the effectiveness of the films was considerably greater in diluted growth media. Furthermore, no significant differences were found either in the antimicrobial capacities of films incorporating different amounts of silver or in the amount of silver that migrated into the liquid media after 18 h of immersion of the film. Neutralized films maintained their activity after 1 month of immersion in deionized water, which can be attributed to the slow sustained release of silver ions and thus efficacy over time.
In this work, cinnamaldehyde was reversibly anchored to chitosan films via imino-covalent bonding. The Schiff base was synthesized in solid phase employing neutralized chitosan films immersed in ...acidified 95 % (v/v) ethanolic solution in which the aldehyde was dissolved. The substitution degree (%) of cinnamaldehyde to the amine group was close to 70 %. Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR) analysis revealed the formation of the chitosan-cinnamaldehyde Schiff base. The hydrolysis of the imino bond and subsequent release of cinnamaldehyde were studied after the films had been subjected to different combinations of temperature/time treatments simulating food preservation methods. The amount of aldehyde that remained covalently attached to the films was monitored by ATR-FTIR, and the substitution degree was determined by elemental analysis. Surface contact angle and colour parameters of cinnamaldehyde-imine-chitosan films and these films subjected to different treatments were also evaluated. The antimicrobial properties of chitosan-Schiff base films were tested in vitro against Staphylococcus aureus and Escherichia coli and in milk inoculated with Listeria monocytogenes. The antimicrobial activity varied depending on the treatment applied and consequently the degree of imino bond hydrolysis achieved and cinnamaldehyde released. Films of Schiff base-chitosan derivative subjected to different time/temperature treatments inhibited the growth of L. monocytogenes for 12 days under refrigeration conditions, which may extend the microbiological shelf life of such products. Sensory analysis of milk in contact with the films showed that a cinnamon smell does not cause any rejection among potential consumers. These novel films could be used in the design of antimicrobial food packaging and in various other technological areas where sustained-release systems are required.