A novel and efficient strategy for the biodegradation of di(2-ethylhexyl) phthalate by Fusarium culmorum.

Di(2-ethylhexyl) phthalate (DEHP) is a plasticizer that is used worldwide and raises concerns because of its prevalence in the environment and potential toxicity. Herein, the capability of Fusarium culmorum to degrade a high concentration (3 g/L) of DEHP as the sole carbon and energy source in solid-state fermentation (SSF) was studied. Cultures grown on glucose were used as controls. The biodegradation of DEHP by F. culmorum reached 96.9% within 312 h. This fungus produced a 3-fold higher esterase activity in DEHP-supplemented cultures than in control cultures (1288.9 and 443.2 U/L, respectively). In DEHP-supplemented cultures, nine bands with esterase activity (24.6, 31.2, 34.2, 39.5, 42.8, 62.1, 74.5, 134.5, and 214.5 kDa) were observed by zymography, which were different from those in control cultures and from those previously reported for cultures grown in submerged fermentation. This is the first study to report the DEHP biodegradation pathway by a microorganism grown in SSF. The study findings uncovered a novel biodegradation strategy by which high concentrations of DEHP could be biodegraded using two alternative pathways simultaneously. F. culmorum has an outstanding capability to efficiently degrade DEHP by inducing esterase production, representing an ecologically promising alternative for the development of environmental biotechnologies, which might help mitigate the negative impacts of environmental contamination by this phthalate. KEY POINTS: • F. culmorum has potential to tolerate and remove di(2-ethylhexyl) phthalate (DEHP) • Solid-state fermentation is an efficient system for DEHP degradation by F. culmorum • High concentrations of DEHP induce high levels of esterase production by F. culmorum.

NADES blend for bioactive coating design as a sustainable strategy for postharvest control.

Bioactive functional coatings constitute a trendy topic due to they reduce postharvest fruit losses worldwide. Also, they could be carriers of biocompounds providing health benefits to the consumer. In this work, an innovative natural bioactive coating based on Natural Deep Eutectic Solvents (NADES) and Larrea divaricata extract was optimized by mixture-mixture design for the management of postharvest diseases caused by Monilinia fructicola. A NADES composed of lactic acid-glucose-water (LGH) for phenolic extraction from L. divaricata was optimized by a Simplex Lattice design and response surface methodology (RSM).Then, a d-optimal mixture-mixture design was carried out in order to optimize the bioactive coating composition, being the optimal proportion of 0.7 L. divaricata-LGH extract and 0.3 NADES plasticizer (composed by glycerol, citric acid and water). The optimal biocoating achieved an in vitro antimicrobial activity of 72 % against M. fructicola. Interestingly, NADES plasticizer improves the biocoating functionality, creating a smooth and uniform surface.

PHB Processability and Property Improvement with Linear-Chain Polyester Oligomers Used as Plasticizers.

In 2021, global petroleum-based plastic production reached over 400 million metric tons (Mt), and the accumulation of these non-biodegradable plastics in the environment is a worldwide concern. Polyhydroxybutyrate (PHB) offers many advantages over traditional petroleum-based plastics, being biobased, completely biodegradable, and non-toxic. However, its production and use are still challenging due to its low deformation capacity and narrow processing window. In this work, two linear-chain polyester oligomers were used as plasticizers to improve the processability and properties of PHB. Thermal analyses, XRD, and polarized optical microscopy were performed to evaluate the plasticizing effect on the PHB and the reflection on the mechanical behavior. Both oligomers acted as PHB plasticizers, with a reduction in Tg and Tm as a function of the plasticizer concentration, which can make it easier to handle the material in thermal processing and reduce the probability of thermal degradation. Plasticizer 2 proved to be the most promising between the two with an optimized condition of 20%, in which there was a decrease in elastic modulus of up to 72% and an increase in the maximum elongation of 467%.

Effect of Plasticizer Content on Mechanical and Water Vapor Permeability of Maize Starch/PVOH/Chitosan Composite Films.

Packaging materials based on biodegradable polymers are a viable alternative to replace conventional plastic packaging from fossil origin. The type of plasticizer used in these materials affects their functionality and performance. The effect of different plasticizers such as glycerol (GLY), sorbitol (SOR), and poly(ethylene glycol) (PEG) in concentrations of 5%, 10%, and 15% (w/w) on the structural features and functional properties of starch/PVOH/chitosan films was evaluated. The incorporation of a plasticizer increased the thickness of the biodegradable composite films. Furthermore, the material plasticized with 30% (w/w) sorbitol had the highest elongation at break, lowest water vapor permeability, and better thermal resistance. The results obtained in this study suggest that maize starch/PVOH/chitosan biodegradable composite films are a promising packaging material, and that sorbitol is the most suitable plasticizer for this formulation.

Chitosan as a Valuable Biomolecule from Seafood Industry Waste in the Design of Green Food Packaging.

Chitosan is a versatile biomolecule with a broad range of applications in food and pharmaceutical products. It can be obtained by the alkaline deacetylation of chitin. This biomolecule can be extracted using conventional or green methods from seafood industry residues, e.g., shrimp shells. Chitin has limited applications because of its low solubility in organic solvents. Chitosan is soluble in acidified solutions allowing its application in the food industry. Furthermore, biological properties, such as antioxidant, antimicrobial, as well as its biodegradability, biocompatibility and nontoxicity have contributed to its increasing application as active food packaging. Nevertheless, some physical and mechanical features have limited a broader range of applications of chitosan-based films. Green approaches may be used to address these limitations, leading to well-designed chitosan-based food packaging, by employing principles of a circular and sustainable economy. In this review, we summarize the properties of chitosan and present a novel green technology as an alternative to conventional chitin extraction and to design environmentally friendly food packaging based on chitosan.

Evaluation of the Factors Affecting the Disintegration under a Composting Process of Poly(lactic acid)/Poly(3-hydroxybutyrate) (PLA/PHB) Blends.

The overall migration behavior and the disintegration under composting conditions of films based on plasticized poly(lactic acid)/poly(3-hydroxybutyrate) (PLA-PHB) blends were studied, with the main aim of determining the feasibility of their application as biodegradable food packaging materials. The role of composition in the disintegration process was evaluated by monitoring the changes in physical and thermal properties that originated during the degradation process. PLA and PHB were blended in two weight ratios with 15 wt% of tributyrin, using a Haake mixer and then compression molded into ~150 µm films. We found that the migration level of all of the studied blends was below check intended meaning retained in non-polar simulants, while only plasticized blends could withstand the contact with polar solvents. The disintegration of all of the materials in compost at 58 °C was completed within 42 days; the plasticized PHB underwent the fastest degradation, taking only 14 days. The presence of the TB plasticizer speeded up the degradation process. Different degradation mechanisms were identified for PLA and PHB. To evaluate the annealing effect separately from bacteria degradation, the influence of temperature on materials in the absence of a compost environment was also studied. With the increasing time of degradation in compost, both melting temperature and maximum degradation temperature progressively decreased, while the crystallinity degree increased, indicating that the samples were definitely degrading and that the amorphous regions were preferentially eroded by bacteria.

Structural Characterization of the Plasticizers' Role in Polymer Inclusion Membranes Used for Indium (III) Transport Containing IONQUEST® 801 as Carrier.

Polymer inclusion membranes containing cellulose triacetate as support, Ionquest® 801 ((2-ethylhexyl acid) -mono (2-ethylhexyl) phosphonic ester) as extractant, and 2NPOE (o-nitrophenyl octyl ether) or TBEP (tri (2-butoxyethyl phosphate)) as plasticizers were characterized using several instrumental techniques (Fourier Transform Infrared Spectroscopy (FT-IR), Reflection Infrared Mapping Microscopy (RIMM), Electrochemical Impedance Spectroscopy (EIS), Differential Scanning Calorimetry (DSC)) with the aim of determining physical and chemical parameters (structure, electric resistance, dielectric constant, thickness, components' distributions, glass transition temperature, stability) that allow a better comprehension of the role that the plasticizer plays in PIMs designed for In(III) transport. In comparison to TBEP, 2NPOE presents less dispersion and affinity in the PIMs, a plasticizer effect at higher content, higher membrane resistance and less permittivity, and a pronounced drop in the glass transition temperature. However, the increase in permittivity with In (III) sorption is more noticeable and, in general, PIMs with 2NPOE present higher permeability values. These facts indicate that In (III) transport is favored in membranes with chemical environment of high polarity and efficiently plasticized. A drawback is the decrease in stability because of the minor affinity among the components in 2NPOE-PIMs.

Urinary concentrations of phthalate metabolites in pregnant women living near Chapala Lake, Jalisco, Mexico.

Phthalates are esters of phthalic acid used in a broad array of consumer products and food contact surfaces. Phthalates are known endocrine disruptors and oxidant stressors, and exposure has been associated with premature birth, asthma, obesity, insulin resistance and endometriosis. Though many industrializing countries are known to manufacture phthalates, few studies have examined exposure to phthalates in this context, let alone in rural communities where phthalate-containing products are widely used. We evaluated the presence of 16 phthalate metabolites in third trimester pregnant women in three rural communities near the largest lake in Mexico, Lake Chapala, by liquid chromatography coupled to tandem mass spectrometry in 90 urine samples. Phthalate metabolites were found in all samples, where the highest concentration was 1830 ng/mL in mono-ethyl phthalate (mEP), and it was present in 98.9% of all samples. These findings suggest the need for further research on the effect of endocrine disrupting chemicals in developing countries, and public health guidance on opportunities for prevention.

Improved antioxidant activity of a starch and gelatin-based biodegradable coating containing Tetradenia riparia extract.

The incorporation of plant-based extracts into polymer-based coatings is an efficient alternative to increase the shelf-life of stored fruit and to decrease or even prevent bacterial growth. Considering strawberries, it is also important to preserve their high antioxidant activity. Hence, this work evaluated the efficiency of a coating based on native cassava starch (NCS), gelatin, and sorbitol, containing different concentrations of Tetradenia riparia extract, in delaying the ripening process of strawberries stored under refrigerated conditions, and in preventing bacterial growth and antioxidant activity losses. Both concentrations of extract (500 or 1000 µg mL-1) increased the thickness, opacity, and water vapor transmission rate (WVTR) of the films when compared to the film without extract, but decreased the solubility. Even though the film without extract was expected to create a more efficient barrier to the coated fruits, the films containing the extract led to similar results of soluble solids (SS), titratable acidity (TA), and vitamin C. Nevertheless, the extract incorporation improved the control over bacterial growth, and preserved the high antioxidant activity of the strawberries within ten days of storage.

Diminution of migration of phthalic acid esters in tequila beverage by the year of production.

The presence of diethyl-phthalate (DEP), dibutyl-phthalate (DBP), butylbenzyl-phthalate (BBP), diethylhexyl-phthalate (DEHP) and diisononyl-phthalate (DINP) was determined in 295 tequila samples. They were grouped by age of maturation (white, aged, extra aged or ultra aged) and year of production (between 2013 and 2018). Gas Chromatography coupled with Mass Spectrometry was used for identification and quantification. The results showed that 65 samples (22% of the total) were phthalate free. DEP (0.13-0.27 mg/kg), BBP (0.05-2.91 mg/kg) and DINP (1.64-3.43 mg/kg) were detected in 11 (3.73%), 37 (12.54%) and 5 (1.69%) samples, respectively. But, these concentrations did not exceed the maximum permitted limits (MPL) of phthalates for alcoholic beverages. DBP (0.01-2.20 mg/kg) and DEHP (0.03-4.64 mg/kg) were detected in 96 (32.54%) and 224 (75.93%) samples, from them only 10 (3.39%) and 15 (5.08%) samples, respectively, exceeded the MPL for alcoholic beverages and they were few tequilas produced in the year 2014 or before. DEHP was the most frequent phthalate found in tequila and observed DEHP concentrations were 2-times higher in ultra aged tequilas compared to those in white tequilas. We concluded that all tequilas produced in 2015 and after, satisfied the international standards for these compounds.

Role of urea and melamine as synergic co-plasticizers for starch composites for fertilizer application.

Herein we describe the interaction of starch, urea, and melamine (C3N6H6) in composite materials for use as controlled-release plant fertilizer. Slow-release fertilizers are important in minimizing nutrient losses due to run-off, leaching, and other factors. Urea is an effective plasticizer for starch and is an important nitrogen fertilizer throughout the world. Melamine also has high nitrogen content and could be combined with urea-starch composites to provide enhanced controlled-release fertilizer. This study reports the structural interaction and the performance gain of melamine addition to starch-urea composites. Composites were characterized by spectroscopic techniques (FT-Raman and 13C NMR) detailing the interaction between melamine, urea, and starch. These interactions helped facilitate extrusion processing by lowering viscosity and processing temperatures suggesting an enhanced starch plasticizing effect of starch-urea-melamine composites. Further research into the co-plasticization of starch by urea and melamine could be exploited for improved controlled-release fertilizer products. Further research into the co-plasticization of starch by urea and melamine could be exploited for improved controlled-release fertilizer products.

Bio-based thin films of cellulose nanofibrils and magnetite for potential application in green electronics.

The objective of this work was to prepare bio-based thin films and evaluate the additions of magnetite and glycerol on the physico-chemical (flexibility, wettability and barrier properties) and dielectric properties of cellulose/chitosan-based films. The films were prepared by solution casting and presented a suitable dispersion of the constituents observed by SEM and FTIR. The films were thermally stable up to 150 °C and had a higher flexibility, wettability and lower barrier properties upon addition of glycerol. The calculated dielectric constant (εr) for the composite films was based on measurements of capacitance, at 100 and 1000 Hz, with the additions of magnetite and glycerol more than doubling the εr increasing the charge storage capacity. The bio-based thin films have potential to be used as insulators in capacitors on the production of green electronics thus, reducing toxic and nonrenewable e-waste generation.

Kinetics and pathway of biodegradation of dibutyl phthalate by Pleurotus ostreatus.

Dibutyl phthalate (DBP) is a plasticizer, whose presence in the environment as a pollutant has attained a great deal of attention due to its reported association with endocrine system disturbances on animals. Growth parameters, glucose uptake, percentage of removal efficiency (%E) of DBP, biodegradation constant of DBP (k) and half-life of DBP biodegradation (t1/2) were evaluated for Pleurotus ostreatus grown on media containing glucose and different concentrations of DBP (0, 500 and 1000 mg l-1). P. ostreatus degraded 99.6 % and 94 % of 500 and 1000 mg of DBP l-1 after 312 h and 504 h, respectively. The k was 0.0155 h-1 and 0.0043 h-1 for 500 and 1000 mg of DBP l-1, respectively. t1/2 was 44.7 h and 161 h for 500 and 1000 mg of DBP l-1, respectively. Intermediate compounds of biodegraded DBP were identified by GC-MS and a DBP biodegradation pathway was proposed using quantum chemical calculation. DBP might be metabolized to benzene and acetyl acetate, the first would be oxidated to muconic acid and the latter would enter into the Krebs cycle. P. ostreatus has the ability to degrade DBP and utilizes it as source of carbon and energy.

Edible methylcellulose-based films containing fructo-oligosaccharides as vehicles for lactic acid bacteria.

The goal of this work was to investigate the physicochemical properties of methylcellulose (MC) based films as stabilizers of two strains of lactobacilli: Lactobacillus delbrueckii subsp. bulgaricus CIDCA 333 and Lactobacillus plantarum CIDCA 83114. The incorporation of 3% w/v fructo-oligosaccharides (FOS) into the MC film formulation improved the viability of L. delbrueckii subsp. bulgaricus CIDCA 333 after film preparation. L. plantarum CIDCA 83114 was intrinsically more resistant as no viability loss was observed upon preparation of the films in the absence of FOS. Scanning electronic microscopy images also showed a good incorporation of microorganisms without affecting the homogeneity of the films. FTIR spectroscopy provided structural information about the bacteria-loaded films. Water sorption isotherms showed an impervious behavior at low aw but on exceeding 0.7 of aw the film started to dissolve and form syrup, causing a drastic drop of bacterial viability (log N/N0≤-5). Dynamic mechanical analysis (DMA) demonstrated that the incorporation of microorganisms into the MC films had no effect on vitreous transition temperatures. FOS incorporated into the MC films had a plasticizing effect. Microorganism-loaded films were stored at relative humidities (RH) ranging from 11 to 75%. Both strains could be stored at 11% RH for 90days. At 33 and 44% RH L. delbrueckii subsp. bulgaricus CIDCA 333 could be stored up to 15days and L. plantarum CIDCA 83114 up to 45days. At 75% RH only L. plantarum CIDCA 83114 could be equilibrated (log N/N0: -2.05±0.25), but CFU/g films were undetectable after 15days of storage. The results obtained in this work support the use of MC films containing FOS as a good strategy to immobilize lactic acid bacteria, with potential applications in the development of functional foods.

Evaluation of physicochemical properties and in-vitro release profile of glipizide-matrix patch

OBJECTIVES: The aim of the present investigation was to form matrix patches with ethyl cellulose (EC) as the base polymer, polyvinyl pyrrolidone (PVP) as the copolymer, plasticizer with dibutyl phthalate (DBP) or acetyl tributyl citrate (ATBC) and the drug glipizide (gz) by the solvent casting method. Physicochemical properties of the patches and in vitro drug release were determined in a modified Keshary-chien diffusion cell to optimize the patch formulations with the help of experimental data and figures for further studies. TECHNIQUES: EC and PVP of different proportions with different weight percentages of either DBP or ATBC and a fixed amount of glipizide were taken for matrix patch formations. The dried patches were used for measuring their drug contents as well as their thicknesses, tensile strengths, moisture contents and water absorption amounts in percentage. In vitro release amounts at different intervals were measured by UV-spectrophotometer. RESULTS: Drug contents varied from 96 - 99 percent. Thickness and tensile strength varied due to weight variation of the ingredients in the matrix patches. Moisture content and water absorption in wt percent were greater for the patches containing higher amount of PVP due to its hydrophilic nature. Variations in drug release were observed among various formulations. It was found that all of the releases followed diffusion controlled zero order kinetics. Two DBP patches yielded better and more adequate release. CONCLUSIONS: The two formulations with DBP were the preferred choice for making matrix patches for further studies.

O objetivo da presente pesquisa foi formar matrizes para bandagens de liberação transdérmica com etilcelulose (EC) como polímero base, polivinilpirrolidona (PVP), como copolímero, plastificante com ftalato de dibutila (DBP) ou citrato de tributilacetila (ATBC) e o fármaco glipizida (gz) pelo método de evaporação do solvente (moldagem com solvente). As propriedades físico-químicas das bandagens e a liberação do fármaco in vitro na célula de difusão de Keshary-chien modificada foram determinadas para aperfeiçoar as formulações das bandagens com o auxílio de dados experimentais e figuras para estudos posteriores. EC e PVP em diferentes proporções com porcentagens diferentes de massa tanto de DBP quanto de ATBC e quantidade fixa de glipizida foram utilizadas como matrizes para a formação de bandagens de liberação transdérmica. As bandagens secas foram empregadas para medir seus conteúdos em fármaco e, também, a sua espessura, resistência à tensão, conteúdos de umidade e porcentagem de absorção de água. As quantidades liberadas in vitro em diferentes intervalos de tempo foram medidas por espectrofotômetro de UV. Os conteúdos de fármaco variaram de 96 a 99 por cento. A espessura e a resistência à ruptura variaram devido à variação de massa dos componentes da matriz das bandagens. O conteúdo de umidade e a água absorvida, em porcentagem de massa, foram maiores para as bandagens que continham grandes quantidades de PVP devido à sua natureza hidrofílica. As variações na liberação de fármaco foram observadas entre as várias formulações. Todas as liberações seguiram a cinética de difusão controlada de ordem zero. Duas bandagens DBP resultaram em melhor e mais adequada liberação. As duas formulações com DBP foram escolhidas para a preparação de matriz de bandagens para estudos posteriores.

Film forming capacity of chemically modified corn starches.

Native starch can be chemically modified to improve its functionality and to expand its uses. Modified starches were characterized and the rheological behavior of filmogenic suspensions was analyzed. The film forming capacity of different chemical modified corn starches was evaluated. Acetylated starch was selected by the characteristics of the resulted films; its optimum concentration was 5% w/w since their films exhibited the lowest water vapor permeability (WVP, 1.26×10(-10)g/msPa). The effect of glycerol as plasticizer on film properties depend on its concentration, being 1.5% w/w those that allows to obtain the lowest WVP value (1.64×10(-11)g/msPa), low film solubility in water and a more compact structure than those of unplasticized films. Mechanical behavior of plasticized acetylated starch films depends on glycerol concentration, being rigid and brittle the unplasticized ones, ductile those containing 1.5% w/w of glycerol and very flexible those with a higher plasticizer content.