Development of novel nano-biocomposite antioxidant films based on poly (lactic acid) and thymol for active packaging

Novel nano-biocomposite films based on poly (lactic acid) (PLA) were prepared by incorporating thymol, as the active additive, and modified montmorillonite (D43B) at two different concentrations. A complete thermal, structural, mechanical and functional characterization of all nano-biocomposites was carried out. Thermal stability was not significantly affected by the addition of thymol, but the incorporation of D43B improved mechanical properties and reduced the oxygen transmission rate by the formation of intercalated structures, as suggested by wide angle X-ray scattering patterns and transmission electron microscopy images. The addition of thymol decreased the PLA glass transition temperature, as the result of the polymer plasticization, and led to modification of the elastic modulus and elongation at break. Finally, the amount of thymol remaining in these formulations was determined by liquid chromatography (HPLC-UV) and the antioxidant activity by the DPPH spectroscopic method, suggesting that the formulated nano-biocomposites could be considered a promising antioxidant active packaging material.

La Plataforma Triásica Alpujárride (Zonas Internas de la Cordillera Bética, España)

A partir de estudios estratigráficos, centrados en la sucesión triásica alpujárride de la Sierra de Gádor (Almería, Cordillera Bética) y su correlación con otros sectores, proponemos una columna estratigráfica sintética para la Plataforma Triásica Alpujárride. Esta columna estaría dividida en dos formaciones: una metasiliciclástica basal (subdividida en tres miembros: inferior, intermedio y superior) y una metacarbonática suprayacente (subdivididida en seis miembros, numerados del 1 al 6 de muro a techo). Esta plataforma habría sufrido una evolución morfológica en tres fases: Fase 1 de rampa homoclinal (Anisiense-Ladiniense); Fase 2 de plataforma fallada (Ladiniense-Carniense); y Fase 3 de plataforma orlada (Noriense). Además, a partir del análisis sedimentario de las asociaciones de facies reconocidas en la sucesión triásica de la Sierra de Gádor proponemos su división en cuatro secuencias deposicionales para el intervalo comprendido entre el Anisiense y el Noriense. La primera secuencia comprendería los miembros inferior e intermedio de la formación metasiliciclástica; la segunda secuencia deposicional incluiría el miembro superior de la formación metasiliciclástica y los miembros 1 y 2 de la formación metacarbonática; la tercera secuencia constaría de los miembros 3 y 4, mientras que la cuarta secuencia estaría constituida por los miembros 5 y 6.

Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles

Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

Functional properties of sodium and calcium caseinate antimicrobial active films containing carvacrol

Active edible films were prepared by adding carvacrol into sodium caseinate (SC) and calcium caseinate (CC) matrices plasticized with two different glycerol concentrations (25 and 35 wt%) prepared by solvent casting. Functional characterisation of these bio-films was carried out by determination of some of their physico-chemical properties, such as colour, transparency, oxygen barrier, wettability, dye permeation properties and antibacterial effectiveness against Gram negative and Gram positive bacteria. All films exhibited good performance in terms of optical properties in the CIELab space showing high transparency. Carvacrol was able to reduce CC oxygen permeability and slightly increased the surface hydrophobicity. Dye diffusion experiments were performed to evaluate permeation properties. The diffusion of dye through films revealed that SC was more permeable than CC. The agar diffusion method was used for the evaluation of the films antimicrobial effectiveness against Escherichia coli and Staphylococcus aureus. Both SC and CC edible films with carvacrol showed inhibitory effects on both bacteria.

Integration of different models in the design of chemical processes: Application to the design of a power plant

With advances in the synthesis and design of chemical processes there is an increasing need for more complex mathematical models with which to screen the alternatives that constitute accurate and reliable process models. Despite the wide availability of sophisticated tools for simulation, optimization and synthesis of chemical processes, the user is frequently interested in using the ‘best available model’. However, in practice, these models are usually little more than a black box with a rigid input–output structure. In this paper we propose to tackle all these models using generalized disjunctive programming to capture the numerical characteristics of each model (in equation form, modular, noisy, etc.) and to deal with each of them according to their individual characteristics. The result is a hybrid modular–equation based approach that allows synthesizing complex processes using different models in a robust and reliable way. The capabilities of the proposed approach are discussed with a case study: the design of a utility system power plant that has been decomposed into its constitutive elements, each treated differently numerically. And finally, numerical results and conclusions are presented.

Enantioselective Michael addition of isobutyraldehyde to nitroalkenes organocatalyzed by chiral primary amine-guanidines

Primary amine-guanidines derived from trans-cyclohexane-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of isobutyraldehyde to arylated and heteroarylated nitroalkenes. The reaction was performed in the presence of imidazole as the additive in aqueous DMF as the solvent at 0 °C. The corresponding Michael adducts bearing a new stereocenter were obtained in high yields and with enantioselectivities of up to 80%. Theoretical calculations are used to justify the observed sense of the stereoinduction.

Polarimetric Response of Rice Fields at C-Band: Analysis and Phenology Retrieval

A set of ten RADARSAT-2 images acquired in fully polarimetric mode over a test site with rice fields in Seville, Spain, has been analyzed to extract the main features of the C-band radar backscatter as a function of rice phenology. After observing the evolutions versus phenology of different polarimetric observables and explaining their behavior in terms of scattering mechanisms present in the scene, a simple retrieval approach has been proposed. This algorithm is based on three polarimetric observables and provides estimates from a set of four relevant intervals of phenological stages. The validation against ground data, carried out at parcel level for a set of six stands and up to nine dates per stand, provides a 96% rate of coincidence. Moreover, an equivalent compact-pol retrieval algorithm has been also proposed and validated, providing the same performance at parcel level. In all cases, the inversion is carried out by exploiting a single satellite acquisition, without any other auxiliary information.

Crop Phenology Estimation Using a Multitemporal Model and a Kalman Filtering Strategy

In this letter, a new approach for crop phenology estimation with remote sensing is presented. The proposed methodology is aimed to exploit tools from a dynamical system context. From a temporal sequence of images, a geometrical model is derived, which allows us to translate this temporal domain into the estimation problem. The evolution model in state space is obtained through dimensional reduction by a principal component analysis, defining the state variables, of the observations. Then, estimation is achieved by combining the generated model with actual samples in an optimal way using a Kalman filter. As a proof of concept, an example with results obtained with this approach over rice fields by exploiting stacks of TerraSAR-X dual polarization images is shown.

Colloidal gold immobilized on mesoporous silica as a highly active and selective catalyst for styrene epoxidation with H2O2

Colloidal gold nanoparticles were synthesized by different procedures affording suspensions with two different mean sizes (2 and 5 nm). Au catalysts were prepared by sol immobilization onto several silica frameworks with different 2D and 3D mesoporosities. The catalysts were tested in styrene oxidation reactions showing excellent efficiency and selectivity. The effect of nanoparticle size and mesoporous framework on the physical and catalytic properties of the final materials was studied. The most selective catalyst was prepared from the 5 nm Au nanoparticles and the more interconnected silica framework (3D mesoporosity).

Feedbacks between vegetation pattern and resource loss dramatically decrease ecosystem resilience and restoration potential in a simple dryland model

Conceptual frameworks of dryland degradation commonly include ecohydrological feedbacks between landscape spatial organization and resource loss, so that decreasing cover and size of vegetation patches result in higher water and soil losses, which lead to further vegetation loss. However, the impacts of these feedbacks on dryland dynamics in response to external stress have barely been tested. Using a spatially-explicit model, we represented feedbacks between vegetation pattern and landscape resource loss by establishing a negative dependence of plant establishment on the connectivity of runoff-source areas (e.g., bare soils). We assessed the impact of various feedback strengths on the response of dryland ecosystems to changing external conditions. In general, for a given external pressure, these connectivity-mediated feedbacks decrease vegetation cover at equilibrium, which indicates a decrease in ecosystem resistance. Along a gradient of gradual increase of environmental pressure (e.g., aridity), the connectivity-mediated feedbacks decrease the amount of pressure required to cause a critical shift to a degraded state (ecosystem resilience). If environmental conditions improve, these feedbacks increase the pressure release needed to achieve the ecosystem recovery (restoration potential). The impact of these feedbacks on dryland response to external stress is markedly non-linear, which relies on the non-linear negative relationship between bare-soil connectivity and vegetation cover. Modelling studies on dryland vegetation dynamics not accounting for the connectivity-mediated feedbacks studied here may overestimate the resistance, resilience and restoration potential of drylands in response to environmental and human pressures. Our results also suggest that changes in vegetation pattern and associated hydrological connectivity may be more informative early-warning indicators of dryland degradation than changes in vegetation cover.

Characterization and ageing study of poly(lactic acid) films plasticized with oligomeric lactic acid

Poly(lactic acid) (PLA) was melt-blended with a bio-based oligomeric lactic acid (OLA) plasticizer at different concentrations between 15 wt% and 25 wt% in order to enhance PLA ductility and to get a fully biodegradable material with potential application in films manufacturing. OLA was an efficient plasticizer for PLA, as it caused a significant decrease on glass transition temperature (Tg) while improving considerably ductile properties. Only one Tg value was observed in all cases and no apparent phase separation was detected. Films obtained by compression moulding were stored during 3 months under ambient controlled conditions and thermal, mechanical, structural and oxygen barrier properties were studied in order to evaluate the stability of the PLA–OLA films over time. Blends with 20 and 25 wt% OLA remained stable and compatible with PLA within the ageing period. Besides, PLA–20 wt% OLA formulation was the only one which maintained its amorphous state with adequate thermal, mechanical and oxygen barrier properties for flexible films manufacturing.

Combined effects of cellulose nanocrystals and silver nanoparticles on the barrier and migration properties of PLA nano-biocomposites

Poly(lactic acid) (PLA)-based high performance nano-biocomposites were prepared to be used in active food packaging. Pristine (CNC) and surfactant modified cellulose nanocrystals (s-CNC) with silver (Ag) nanoparticles were used as the matrix modifiers. Binary and ternary systems were prepared. Morphological investigations revealed the good distribution of silver nanoparticles in PLA ternary systems. The combination of s-CNC and Ag nanoparticles increased the barrier effect of the produced films while the results of overall migration for the PLA nano-biocomposites revealed that none of the samples exceeded the overall migration limit, since results were well below 60 mg kg−1 of simulant.

Development of a novel pyrolysis-gas chromatography/mass spectrometry method for the analysis of poly(lactic acid) thermal degradation products

Thermal degradation of PLA is a complex process since it comprises many simultaneous reactions. The use of analytical techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), yields useful information but a more sensitive analytical technique would be necessary to identify and quantify the PLA degradation products. In this work the thermal degradation of PLA at high temperatures was studied by using a pyrolyzer coupled to a gas chromatograph with mass spectrometry detection (Py-GC/MS). Pyrolysis conditions (temperature and time) were optimized in order to obtain an adequate chromatographic separation of the compounds formed during heating. The best resolution of chromatographic peaks was obtained by pyrolyzing the material from room temperature to 600 °C during 0.5 s. These conditions allowed identifying and quantifying the major compounds produced during the PLA thermal degradation in inert atmosphere. The strategy followed to select these operation parameters was by using sequential pyrolysis based on the adaptation of mathematical models. By application of this strategy it was demonstrated that PLA is degraded at high temperatures by following a non-linear behaviour. The application of logistic and Boltzmann models leads to good fittings to the experimental results, despite the Boltzmann model provided the best approach to calculate the time at which 50% of PLA was degraded. In conclusion, the Boltzmann method can be applied as a tool for simulating the PLA thermal degradation.

Structure and mechanical properties of sodium and calcium caseinate edible active films with carvacrol

Edible active films based on sodium caseinate (SC) and calcium caseinate (CC) plasticized with glycerol (G) at three different concentrations and carvacrol (CRV) as active agent were prepared by solvent casting. Transparent films were obtained and their surfaces were analysed by optical microscopy and scanning electron microscopy (SEM). The influence of the addition of three different plasticizer concentrations was studied by determining tensile properties, while Fourier transformed infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) were used to evaluate the structural and thermal behavior of such films. The addition of glycerol resulted in a reduction in the elastic modulus and tensile strength, while some increase in the elongation at break was observed. In general terms, SC films showed flexibility higher than the corresponding CC counterparts. In addition, the presence of carvacrol caused further improvements in ductile properties suggesting the presence of stronger interactions between the protein matrix and glycerol, as it was also observed in thermal degradation studies. FTIR spectra of all films showed the characteristic bands and peaks corresponding to proteins as well as to primary and secondary alcohols. In summary, the best results regarding mechanical and structural properties for caseinates-based films containing carvacrol were found for the formulations with high glycerol concentrations.

Structure, gas-barrier properties and overall migration of poly(lactic acid) films coated with hydrogenated amorphous carbon layers

Hydrogenated amorphous carbon (a-C:H) films were grown on a poly(lactic acid) (PLA) substrate by means of a radiofrequency plasma-enhanced chemical vapour deposition (rf-PECVD) technique with different deposition times (5, 20 and 40 min). The main goal of this treatment was to increase the barrier properties of PLA, maintaining its original transparency and colour as well as controlling interactions with food simulants for packaging applications. Morphological, chemical, and mechanical properties of PLA/a-C:H systems were evaluated while permeability and overall migration tests were performed in order to determine the effect of the plasma treatment on the gas-barrier properties of PLA films and their application in food packaging. Morphological results suggested a good adhesion of the deposited layers onto the polymer surface and the samples treated for 5 and 20 min only slightly darkened the PLA film. X-ray photoelectron spectroscopy revealed that the structural properties of the carbon layer deposited onto the PLA film depend on the exposure time. PLA/a-C:H system treated for 5 min showed the highest barrier properties, while none of the studied samples exceeded the migration limit established by the current legislation, suggesting the suitability of these materials in packaging applications.