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1.
Sci Rep ; 14(1): 11161, 2024 05 15.
Article En | MEDLINE | ID: mdl-38750054

Biodegradable plastics are those subjected easily to a degradation process, in which they can be decomposed after disposal in the environment through microbial activity. 30 bioplastic film formulations based only on chitosan film were used in the current investigation as a positive control together with chitosan film recovered from chitin-waste of locally obtained Aristeus antennatus. Additionally, castor oil was used as a plasticizer. While the yield of chitosan was 18% with 7.65% moisture content and 32.27% ash in the shells, the isolated chitin had a degree of deacetylation (DD) of 86%. The synthesized bioplastic films were characterized via numerous criteria. Firstly, the swelling capacity of these biofilms recorded relatively high percentages compared to polypropylene as synthetic plastic. Noticeably, the FTIR profiles, besides DSC, TGA, and XRD, confirmed the acceptable characteristics of these biofilms. In addition, their SEM illustrated the homogeneity and continuity with a few straps of the chitosan film and showed the homogeneous mixes of chitosan and castor oil with 5 and 20%. Moreover, data detected the antibacterial activity of different bioplastic formulas against some common bacterial pathogens (Enterococcus feacalis, Kelbsiella pnumina, Bacillus subtilis, and Pseudomonas aeruginosa). Amazingly, our bioplastic films have conducted potent antimicrobial activities. So, they may be promising in such a direction. Further, the biodegradability efficacy of bioplastic films formed was proved in numerous environments for several weeks of incubation. However, all bioplastic films decreased in their weights and changed in their colors, while polypropylene, was very constant all the time. The current findings suggest that our biofilms may be promising for many applications, especially in the field of food package protecting the food, and preventing microbial contamination, consequently, it may help in extending the shelf life of products.


Biodegradable Plastics , Castor Oil , Chitosan , Plasticizers , Starch , Chitosan/chemistry , Chitosan/pharmacology , Castor Oil/chemistry , Biodegradable Plastics/chemistry , Biodegradable Plastics/pharmacology , Plasticizers/chemistry , Starch/chemistry , Animals , Biofilms/drug effects , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Moths/drug effects , Microbial Sensitivity Tests
2.
Int J Biol Macromol ; 268(Pt 1): 131603, 2024 May.
Article En | MEDLINE | ID: mdl-38626835

The thermoplastic starch with glycerol is easy to retrograde and sensitive to hygroscopicity. In this study, branched 1,4-butanediol citrate oligomers with different molecular weights (P1, P2, and P3) are synthesized, and then mixed with glycerol (G) as the co-plasticizers to prepare thermoplastic starch (CS/PG). The results show that the molecular weight and branching degree of the branched 1,4-butanediol citrate oligomers increase as reaction time prolongs. Compared with glycerol plasticized starch, the thermoplastic starch films with branched 1,4-butanediol citrate oligomers/glycerol (10 wt%/20 wt%) have a better toughness, transmittance, and aging resistance, and have a lower crystallinity, hygroscopicity, and thermal stability. The toughness, transmittance, and aging resistance of CS/PG films are positively correlated with the molecular weight of the branched 1,4-butanediol citrate oligomers. These are due to the fact that the branched 1,4-butanediol citrate oligomer with a high molecular weight could form a stronger hydrogen bond and the more stable cross-linked structure with starch chains than that with a lower molecular weight. The elongation at break of CS/P3G film stored for 3 and 30 d are 98.0 % and 88.1 %, respectively. The mixture of branched butanediol citrate oligomers and glycerol, especially P3/G, has a potential application in the preparation of thermoplastic starch.


Butylene Glycols , Glycerol , Molecular Weight , Plasticizers , Starch , Starch/chemistry , Glycerol/chemistry , Butylene Glycols/chemistry , Plasticizers/chemistry , Temperature , Citrates/chemistry , Plastics/chemistry
3.
Int J Biol Macromol ; 267(Pt 2): 131726, 2024 May.
Article En | MEDLINE | ID: mdl-38688791

The characteristics of multi-hydroxyl structure and strong hydrogen bonding in polyvinyl alcohol (PVA) make its melting point close to its decomposition temperature, causing melt-processing difficulty. In this work, following the plasticization of small-molecule primary plasticizer acetamide, lignin was demonstrated as a green secondary plasticizer in realizing the melt processing and simultaneous reinforcement of PVA. During the plasticization process, lignin was able to combine with the hydroxyl groups of PVA, so as to destroy the hydrogen bonds and regularity of the PVA chains. The synergistic plasticization effect of lignin dramatically reduced the melting point of PVA from 185 °C to 151 °C. The thermal processing window of PVA composites was expanded from 50 °C to roughly 80 °C after introducing lignin. In contrast to acetamide, the addition of lignin significantly increased the tensile strength and Young's modulus of the composites to 71 MPa and 1.34 GPa, respectively. Meanwhile, lignin helped to hinder the migration of acetamide via hydrogen bonds. With the addition of lignin, the composites also displayed enhanced hydrophobicity and excellent UV shielding performance. The strategy of synergistic plasticization of lignin provides a feasible basis for the practical application of lignin in melt-processable PVA materials with good comprehensive properties.


Lignin , Plasticizers , Polyvinyl Alcohol , Tensile Strength , Lignin/chemistry , Polyvinyl Alcohol/chemistry , Plasticizers/chemistry , Hydrogen Bonding , Temperature , Elastic Modulus , Hydrophobic and Hydrophilic Interactions
4.
Int J Biol Macromol ; 264(Pt 2): 130773, 2024 Apr.
Article En | MEDLINE | ID: mdl-38467211

This work reports on the development of starch-rich thermoplastic based formulations produced by using mango kernel flour, avoiding the extraction process of starch from mango kernel to produce these materials. Glycerol, sorbitol and urea at 15 wt% are used as plasticizers to obtain thermoplastic starch (TPS) formulations by extrusion and injection-moulding processes. Mechanical results show that sorbitol and urea allowed to obtain samples with tensile strength and elongation at break higher than the glycerol-plasticized sample, achieving values of 2.9 MPa of tensile strength and 42 % of elongation at break at 53 % RH. These results are supported by field emission scanning electron microscopy (FESEM) micrographs, where a limited concentration of voids was observed in the samples with sorbitol and urea, indicating a better interaction between starch and the plasticizers. Thermogravimetric analysis (TGA) shows that urea and sorbitol increase the thermal stability of TPS in comparison to the glycerol-plasticized sample. Differential scanning calorimetry (DSC) and dynamic-mechanical-thermal analysis (DMTA) verify the increase in stiffness of the sorbitol and urea plasticized TPS and also illustrate an increase in the glass transition temperature of both samples in comparison to the glycerol-plasticized sample. Glass transition temperatures of 45 °C were achieved for the sample with sorbitol.


Mangifera , Plasticizers , Plasticizers/chemistry , Starch/chemistry , Glycerol/chemistry , Flour , Plastics , Sorbitol/chemistry , Urea/chemistry
5.
Int J Biol Macromol ; 264(Pt 1): 130547, 2024 Apr.
Article En | MEDLINE | ID: mdl-38431012

Plasticizers like Bis(2-ethylhexyl)phthalate (DEHP) are commonly used to enhance plastic properties but pose environmental and health risks. This study successfully derived plasticizers X and Y from rice straws, demonstrating efficacy in chitosan polymer coatings. Chitosan-based polymers exhibit exceptional hardness, with a value of 300 MPa, due to their enriched structure and robust chitosan bonding. This surpasses the hardness of DEHP. Zebrafish exposure over 5 days revealed that X and Y had no significant behavioral impact, while DEHP caused noticeable toxic effects. Maternal DEHP exposure reduced placental cell growth, unlike X and Y, which had no adverse effects on uterine differentiation or placenta formation, suggesting their safety in human pregnancy. The successful development of X and Y represents a crucial step towards greener plasticizers, addressing environmental concerns and promoting safer alternatives in various industries.


Chitosan , Diethylhexyl Phthalate , Oryza , Animals , Female , Humans , Pregnancy , Plasticizers/chemistry , Diethylhexyl Phthalate/chemistry , Zebrafish , Placenta , Polymers
6.
Int J Mol Sci ; 25(3)2024 Jan 31.
Article En | MEDLINE | ID: mdl-38338998

Measures to endorse the adoption of eco-friendly biodegradable plastics as a response to the scale of plastic pollution has created a demand for innovative products from materials from Nature. Ionic liquids (ILs) have the ability to disrupt the hydrogen bonding network of biopolymers, increase the mobility of biopolymer chains, reduce friction, and produce materials with various morphologies and mechanical properties. Due to these qualities, ILs are considered ideal for plasticizing biopolymers, enabling them to meet a wide range of specifications for biopolymeric materials. This mini-review discusses the effect of different IL-plasticizers on the processing, tensile strength, and elasticity of materials made from various biopolymers (e.g., starch, chitosan, alginate, cellulose), and specifically covers IL-plasticized packaging materials and materials for biomedical and electrochemical applications. Furthermore, challenges (cost, scale, and eco-friendliness) and future research directions in IL-based plasticizers for biopolymers are discussed.


Chitosan , Ionic Liquids , Ionic Liquids/chemistry , Plasticizers/chemistry , Cellulose/chemistry , Biopolymers , Chitosan/chemistry
7.
Int J Biol Macromol ; 263(Pt 2): 130366, 2024 Apr.
Article En | MEDLINE | ID: mdl-38401589

Polylactic acid (PLA) is a biobased and biodegradable thermoplastic polyester with great potential to replace petroleum-based plastics. However, its poor toughness and slow biodegradation rate affect broad applications of PLA in many areas. In this study, a glycerol triester existing in natural butter, glycerol tributyrate, was creatively explored and compared with previously investigated triacetin and tributyl citrate, as potential plasticizers of PLA for achieving improved mechanical and biodegradation performances. The compatibilities of these agents with PLA were assessed quantitively via the Hansen solubility parameter (HSP) and measured by using different testing methods. The incorporation of these compounds with varied contents ranging from 1 to 30 % in PLA altered thermal, mechanical, and biodegradation properties consistently, and the relationship and impacts of chemical structures and properties of these agents were systematically investigated. The results demonstrated that glycerol tributyrate is a novel excellent plasticizer for PLA and the addition of this triester not only effectively reduced the glass transition, cold crystallization, and melting temperatures and Young's modulus, but also led to a significant improvement in the enzymatic degradation rate of the plasticized PLA. This study paves a way for the development of sustainable and eco-friendly food grade plasticized PLA products.


Dioxanes , Plasticizers , Polymers , Plasticizers/chemistry , Polymers/chemistry , Glycerol , Polyesters/chemistry
8.
Food Chem ; 444: 138375, 2024 Jun 30.
Article En | MEDLINE | ID: mdl-38402735

The growing concern over extending the shelf life of food products, coupled with the escalating environmental impact of synthetic plastic waste, has fuelled a quest for bio-based alternatives in packaging research. In response to this pressing need, our study delves into the synthesis of chitosan-based films incorporating a deep eutectic solvents (DES). Choline chloride and diverse hydrogen bond donors were used as plasticizers, we also explored the active properties of DES integrated into the chitosan (Ch) matrix. The Ch-based films with chlorine chloride: citric acid can prevent the mold spotting up to 29 days longer in comparison to bread wrapped in polyethylene films (PE). The obtained Ch/DES films exhibited mechanical properties comparable to conventional PE (e.g., up to tensile strength of 26 MPa and up to 210% in case of elongation at break). This synthesis approach represents a significant stride towards environmentally friendly packaging materials, aligning with the principles of green chemistry.


Chitosan , Chitosan/chemistry , Plasticizers/chemistry , Deep Eutectic Solvents , Choline/chemistry , Tensile Strength , Solvents/chemistry
9.
Int J Biol Macromol ; 261(Pt 2): 129771, 2024 Mar.
Article En | MEDLINE | ID: mdl-38286386

Plasticizers are active ingredients added to the polymer to increase its workability. Since synthetic plasticizer is not ecofriendly and toxic in nature, it is a real cause for concern. On this basis, our study focuses on plasticizer extraction from plant-based resources. In this research work, Thespesia populnea leaves are utilized for the isolation of biological macromolecules with a plasticizing effect for biofilm applications. This extraction process is done through solvent extraction, amination, slow pyrolysis, and surface catalysis process. The physico-chemical and microstructural characterization of novel plasticizer particles were studied for the first time. The lower crystallinity index and crystalline size obtained from X-ray diffraction is 50.08 % and 20.45 nm respectively. Energy dispersive spectroscopy, particle sizer analysis, atomic force microscopy, and scanning electron microscopy are used to assess surface morphology of this plasticizer. The thermogram and differential thermal analysis curves give the information about degradation behavior of plasticizers and their thermal stability. The glass transition temperature of the extracted plasticizer is 60.56 °C. The plasticizing effect of the plasticizer is studied through film fabrication of polylactic acid which was blended with the extracted plasticizer. The mechanical property of biofilm was improved with the addition of plasticizer. The elongation break percentage (for 5 % plasticizer 46.12 %) was increased compared to others with moderate tensile strength. However, the tensile and elongation modulus decreases with the increase of plasticizer content. The crystallinity of the PLA film was improved after the plasticization. The thermal stability also increased with 3 % addition of the plasticizer. The isolated plasticizer was soluble in water and its molecular weight ≈380.


Plasticizers , Polyesters , Plasticizers/chemistry , Polyesters/chemistry , Polymers/chemistry , Water/chemistry
10.
Int J Biol Macromol ; 258(Pt 2): 129304, 2024 Feb.
Article En | MEDLINE | ID: mdl-38262823

Chitosan-based bioplastics are attractive biodegradable alternatives to petroleum-derived plastics. However, optimizing the properties of chitosan materials to fit a particular application or obtain a desired property is not a trivial feat. Here, we report the tunability of glycerol-plasticized chitosan films with the addition of boric acid. In combination, glycerol and boric acid form neutral complexes that alter the hydrogen-bonding face of the plasticizer and ultimately limit glycerol's ability to plasticize chitosan. Thus, we found that chitosan films containing glycerol-boric acid complexes were less flexible, had increased thermal transition temperatures, and showed more uniform morphologies. Structural, thermal, mechanical and morphological characterization was performed using ATR-FTIR, TGA and DSC, DMA, and SEM respectively. Molecular-level interactions of the neutral boron complexes and D-glucosamine, the repeat unit of chitosan, were also investigated used NMR and ATR-FTIR. The results of this work demonstrate the necessity of specific hydrogen-bonding interactions between the plasticizer and the polymer for effective plasticization, an important insight into the plasticization mechanism of chitosan films. Furthermore, the formation of complexes with glycerol is a novel and convenient method for tuning the physical properties of chitosan films.


Boric Acids , Chitosan , Chitosan/chemistry , Plasticizers/chemistry , Glycerol/chemistry , Hydrogen
11.
Food Chem ; 438: 137977, 2024 Apr 16.
Article En | MEDLINE | ID: mdl-37976874

Films based on poly(vinyl alcohol) (PVA) and cationic starch (CS) were combined with different percentages of sorbitol (S; 15.0, 22.5, and 30.0% w v-1) to assess the effect of plasticizer on the films. Spectroscopic analyses confirmed the interaction between them. However, micrographs indicated the formation of sorbitol crystals on the surface of the films, especially at higher sorbitol concentrations. The blends presented low water vapor transmission rate values, reaching (7.703 ± 0.000) g h-1 m-2 (PVA75CS25S15), and low solubility values for the films containing higher CS amounts. The lack of statistical differences in most parameters suggests that no significant gain comes from increasing the amount of sorbitol at percentages higher than 15%. As a coating, the blend PVA75CS25S15 successfully decreased the loss of moisture content in acerolas by 1.15 times (compared to the control), confirming the suitability of this matrix as a fruit coating.


Polyvinyl Alcohol , Starch , Starch/chemistry , Polyvinyl Alcohol/chemistry , Plasticizers/chemistry , Spectrum Analysis , Ethanol , Sorbitol
12.
J Pharm Sci ; 113(3): 725-734, 2024 03.
Article En | MEDLINE | ID: mdl-37690776

This study proposes the application of carboxymethyl starch derivatives as tablet coatings affording gastro-protection. Carboxymethyl starch (CMS) films were obtained by casting of aqueous filmogenic starch solutions with or without plasticizers and their structural organization was followed using Fourier transform infrared (FTIR), Thermogravimetric analysis (TGA), X-ray diffraction (XRD). Together with data from mechanical tests (tensile strength, elongation, Young's modulus) the results were used to select filmogenic formulations adapted for coatings of tablets. The behaviour of these films was evaluated in simulated gastric and intestinal fluids. The effect of plasticizers (glycerol and sorbitol) on the starch organization, on the rate of drying of the films and on the water vapor absorption was also analyzed. Various types of starch have been compared and the best results were found with high amylose starch (HAS) that was carboxymethylated in an aqueous phase to obtain carboxymethyl high amylose starch (CMHAS). The CMHAS coating solutions containing sorbitol or glycerol as plasticizers have been applied with an industrial pan coater and the final tablets exhibited a good gastro-resistance (up to 2h) in simulated gastric fluid followed by disintegration in simulated intestinal fluid (SIF). The CMHAS derivatives present a high potential as coatings for nutraceutical and pharmaceutical solid dosage forms.


Amylose , Plasticizers , Starch/analogs & derivatives , Amylose/chemistry , Plasticizers/chemistry , Glycerol/chemistry , Starch/chemistry , Tablets , Sorbitol
13.
Int J Biol Macromol ; 256(Pt 1): 128436, 2024 Jan.
Article En | MEDLINE | ID: mdl-38016616

The development of alternative materials to replace plastics used in food packaging is an important approach to reducing environmental pollution and minimizing harmful impacts on ecosystems. In this study, biopolymeric films were formulated using cassava starch (Manihot esculenta Crantz), pea flour (Pisum sativum) and green banana flour (Musa sp.) to obtain a material for application in food packaging. The influence of a plasticizer on the optical and physicochemical properties of the films was analyzed and the synergy between higher concentrations of starch and plasticizer resulted in films with low opacity. In addition, the morphology, thermal, mechanical and barrier properties were examined. The film with the best formulation (p < 0.05) contained 12 g cassava starch, 3.6 g pea flour and 30 % glycerol (the maximum levels of the experiment). This film presented average values of thickness, moisture, solubility, opacity, maximum strength (F), maximum tensile stress (σ), elongation at break (ε) and elasticity (E) of 0.47 mm, 19.95 %, 87.45 %, 20.93 %, 9.30 N, 1.75 MPa, 30.10 % and 5.93 %, respectively. This research demonstrates the potential application of films obtained by combining starches from different sources. The sustainable production of environmentally-friendly packaging provides an alternative to fossil-based plastics, which have well-documented adverse effects on the environment.


Manihot , Musa , Food Packaging/methods , Pisum sativum , Manihot/chemistry , Flour , Plasticizers/chemistry , Ecosystem , Permeability , Polymers , Starch/chemistry
14.
Int J Pharm ; 643: 123254, 2023 Aug 25.
Article En | MEDLINE | ID: mdl-37473975

Medical devices (MD) are often made of plasticized polyvinylchloride (PVC). However, plasticizers may leach out into infused solutions and expose the patients to a toxic risk. The aim of the present work is to fluorinate plasticized PVC tubular MDs to create a barrier layer on their internal surface, and to study the impact of such a chemical treatment on the migration of the plasticizers. Following fluorination by pure molecular fluorine, the physico-chemical characterization of these modified MDs was carried out using various spectroscopic and microscopic techniques or tensile tests, evidencing the formation of covalent C-F bonds on the surface of the treated samples without modification of their mechanical and optical properties. The migration of plasticizers from fluorinated MDs was assessed using gas chromatography coupled with mass spectrometry and was found considerably decreased in comparison with the pristine MDs. After 24 h, the amount of tri-octyltrimellitate plasticizer (TOTM) detected in migrates from fluorinated MDs was even lower than the limit of quantification. Complementary cytotoxicity assays were performed according to the ISO EN 10993-5 standard, showing that the new fluorinated material does not cause a cytotoxic effect on L929 cells.


Diethylhexyl Phthalate , Plasticizers , Humans , Plasticizers/chemistry , Halogenation , Gas Chromatography-Mass Spectrometry/methods , Polyvinyl Chloride/chemistry , Mass Spectrometry , Diethylhexyl Phthalate/toxicity , Diethylhexyl Phthalate/analysis , Diethylhexyl Phthalate/chemistry
15.
Molecules ; 28(13)2023 Jun 30.
Article En | MEDLINE | ID: mdl-37446807

Supramolecular gemifloxacin (GF) sensors have been developed. Supramolecular chemistry is primarily concerned with noncovalent intermolecular and intramolecular interactions, which are far weaker than covalent connections, but they can be exploited to develop sensors with remarkable affinity for a target analyte. In order to determine the dose form of the quinolone antibacterial drug gemifloxacin, the current study's goal is to adapt three polyvinylchloride (PVC) membrane sensors into an electrochemical technique. Three new potentiometric membrane sensors with cylindric form and responsive to gemifloxacin (GF) were developed. The sensors' setup is based on the usage of o-nitrophenyl octyl ether (o-NPOE) as a plasticizer in a PVC matrix, ß-cyclodextrin (ß-CD) (sensor 1), γ-cyclodextrin (γ-CD) (sensor 2), and 4-tert-butylcalix[8]arene (calixarene) (sensor 3) as an ionophore, potassium tetrakis (4-chlorophenyl) borate (KTpClPB) as an ion additive for determination of GF. The developed method was verified according to IUPAC guidelines. The sensors under examination have good selectivity for GF, according to their selectivity coefficients. The constructed sensors demonstrated a significant response towards to GF over a concentration range of 2.4 × 10-6, 2.7 × 10-6, and 2.42 × 10-6 mol L-1 for sensors 1, 2, and 3, respectively. The sensors showed near-Nernstian cationic response for GF at 55 mV, 56 mV, and 60 mV per decade for sensors 1, 2, and 3, respectively. Good recovery and relative standard deviations during the day and between days are displayed by the sensors. They demonstrated good stability, quick response times, long lives, rapid recovery, and precision while also exhibiting good selectivity for GF in various matrices. To determine GF in bulk and dose form, the developed sensors have been successfully deployed. The sensors were also employed as end-point indicators for titrating GF with sodium tetraphenyl borate.


Borates , Plasticizers , Gemifloxacin , Plasticizers/chemistry , Tetraphenylborate/chemistry , Anti-Bacterial Agents , Potentiometry/methods
16.
PLoS One ; 18(7): e0288491, 2023.
Article En | MEDLINE | ID: mdl-37440506

Phthalate plasticizers are incorporated into plastics to make them soft and malleable, but are known to leach out of the final product into their surroundings with potential detrimental effects to human and ecological health. The replacement of widely-used phthalate plasticizers, such as di-ethylhexyl phthalate (DEHP), that are of known toxicity, by the commercially-available alternative Tris(2-ethylhexyl) tri-mellitate (TOTM) is increasing. Additionally, several newly designed "green" plasticizers, including di-heptyl succinate (DHPS) and di-octyl succinate (DOS) have been identified as potential replacements. However, the impact of plasticizer exposure from medical devices on patient recovery is unknown and, moreover, the safety of TOTM, DHPS, and DOS is not well established in the context of patient recovery. To study the direct effect of clinically based chemical exposures, we exposed C57bl/6 N male and female mice to DEHP, TOTM, DOS, and DHPS during recovery from cardiac surgery and assessed survival, cardiac structure and function, immune cell infiltration into the cardiac wound and activation of the NLRP3 inflammasome. Male, but not female, mice treated in vivo with DEHP and TOTM had greater cardiac dilation, reduced cardiac function, increased infiltration of neutrophils, monocytes, and macrophages and increased expression of inflammasome receptors and effectors, thereby suggesting impaired recovery in exposed mice. In contrast, no impact was detected in female mice and male mice exposed to DOS and DHPS. To examine the direct effects in cells involved in wound healing, we treated human THP-1 macrophages with the plasticizers in vitro and found DEHP induced greater NLRP3 expression and activation. These results suggest that replacing current plasticizers with non-phthalate-based plasticizers may improve patient recovery, especially in the male population. In our assessment, DHPS is a promising possibility for a non-toxic biocompatible plasticizer.


Diethylhexyl Phthalate , Myocardial Infarction , Male , Humans , Mice , Animals , Plasticizers/toxicity , Plasticizers/chemistry , Diethylhexyl Phthalate/toxicity , Succinic Acid , Inflammasomes , NLR Family, Pyrin Domain-Containing 3 Protein , Succinates , Mice, Inbred Strains
17.
Sci Rep ; 13(1): 11530, 2023 07 17.
Article En | MEDLINE | ID: mdl-37460643

Due to the growing demand for robust and environmentally friendly antimicrobial packaging materials, biopolymers have recently become extensively investigated. Although biodegradable biopolymers usually lack mechanical properties, which makes it inevitable to blend them with plasticizers. The purpose of this study was to investigate plasticization efficiency of bio-based plasticizers introduced into sodium alginate compositions containing chestnut extract and their effect on selected film properties, including primarily mechanical and antibacterial properties. The films were prepared by the casting method and sodium alginate was cross-linked with calcium chloride. Six different plasticizers, including three commercially available ones (glycerol, epoxidized soybean oil and palm oil) and three synthesized plasticizers that are mixtures of bio-based plasticizers, were used to compare their influence on the film properties. Interactions between the polymer matrix and the plasticizers were investigated using Fourier transform infrared spectroscopy. The morphological characteristics of the films were characterized by scanning electron microscopy. Thermal properties, tensile strength, elongation at break, hydrophilic, and barrier properties of the obtained films were also determined. To confirm the obtaining of active films through the use of chestnut extract and to study the effect of the proposed plasticizers on the antibacterial activity of the extract, the obtained films were tested against bacteria cultures. The final results showed that all of the obtained films exhibit a hydrophilic character and high barrier effect to oxygen, carbon dioxide and water vapor. In addition, sodium alginate films prepared with chestnut extract and the plasticizer proposed by us, showed better mechanical and antimicrobial properties than the films obtained with chestnut extract and the commercially available plasticizers.


Anti-Infective Agents , Plasticizers , Plasticizers/chemistry , Alginates/chemistry , Polymers , Anti-Bacterial Agents/pharmacology , Anti-Infective Agents/pharmacology , Tensile Strength
18.
Int J Mol Sci ; 24(11)2023 Jun 01.
Article En | MEDLINE | ID: mdl-37298596

A [3 + 2] cycloaddition reaction using dialkyne and diazide comonomers, both bearing explosophoric groups, to synthesize energetic polymers containing furazan and 1,2,3-triazole ring as well as nitramine group in the polymer chain have been described. The developed solvent- and catalyst-free approach is methodologically simple and effective, the comonomers used are easily available, and the resulting polymer does not need any purification. All this makes it a promising tool for the synthesis of energetic polymers. The protocol was utilized to generate multigram quantities of the target polymer, which has been comprehensively investigated. The resulting polymer was fully characterized by spectral and physico-chemical methods. Compatibility with energetic plasticizers, thermochemical characteristics, and combustion features indicate the prospects of this polymer as a binder base for energetic materials. The polymer of this study surpasses the benchmark energetic polymer, nitrocellulose (NC), in a number of properties.


Polymers , Triazoles , Polymers/chemistry , Triazoles/chemistry , Plasticizers/chemistry , Aniline Compounds
19.
Microbiol Spectr ; 11(4): e0480122, 2023 08 17.
Article En | MEDLINE | ID: mdl-37318352

Phthalate diesters are extensively used as plasticizers in manufacturing plastic materials; however, because of their estrogenic properties, these chemicals have emerged as a global threat to human health. The present study investigated the course of degradation of a widely used plasticizer, benzyl butyl phthalate (BBP), by the bacterium PAE-6, belonging to the genus Rhodococcus. The metabolism of BBP, possessing structurally dissimilar side chains, was evaluated biochemically using a combination of respirometric, chromatographic, enzymatic, and mass-spectrometric analyses, depicting pathways of degradation. Consequently, the biochemical observations were corroborated by identifying possible catabolic genes from whole-genome analysis, and the involvement of inducible specific esterases and other degradative enzymes was validated by transcriptomic, reverse transcription-quantitative PCR (RT-qPCR) and proteomic analyses. Nonetheless, phthalic acid (PA), an intermediate of BBP, could not be efficiently metabolized by strain PAE-6, although the genome contains a PA-degrading gene cluster. This deficiency of complete degradation of BBP by strain PAE-6 was effectively managed by using a coculture of strains PAE-6 and PAE-2. The latter was identified as a Paenarthrobacter strain which can efficiently utilize PA. Based on sequence analysis of the PA-degrading gene cluster in strain PAE-6, it appeared that the alpha subunit of the multicomponent phthalate 3,4-dioxygenase harbors a number of altered residues in the multiple sequence alignment of homologous subunits, which may play a role(s) in poor turnover of PA. IMPORTANCE Benzyl butyl phthalate (BBP), an estrogenic, high-molecular-weight phthalic acid diester, is an extensively used plasticizer throughout the world. Due to its structural rigidity and hydrophobic nature, BBP gets adsorbed on sediments and largely escapes the biotic and abiotic degradative processes of the ecosystem. In the present study, a potent BBP-degrading bacterial strain belonging to the genus Rhodococcus was isolated that can also assimilate a number of other phthalate diesters of environmental concern. Various biochemical and multi-omics analyses revealed that the strain harbors all the required catabolic machinery for the degradation of the plasticizer and elucidated the inducible regulation of the associated catabolic genes and gene clusters.


Plasticizers , Rhodococcus , Humans , Plasticizers/chemistry , Plasticizers/metabolism , Rhodococcus/genetics , Rhodococcus/metabolism , Proteomics , Ecosystem , Multiomics
20.
Int J Biol Macromol ; 244: 125478, 2023 Jul 31.
Article En | MEDLINE | ID: mdl-37336376

Thermoplastic starch/polyvinyl alcohol (TPS/PVA) films have limitations for being used in long-term applications due to starch retrogradation. This leads to plasticizer migration, especially when low molecular weight plasticizers such as glycerol, are used. In this work, we employed mixtures of oligomers based on glycerol citrates with higher molecular weight than glycerol as plasticizers for potato-based TPS/PVA blends obtained by melt-mixing. This constitutes an alternative to reduce plasticizer migration while keeping high swelling degree, and to provide high mechanical performance. The novelty lies in the usage of these oligomers by melt-mixing technique, aspect not deeply explored previously and that represents the first step towards industrial scalability. Prior to the blending process, oligomers mixtures were prepared with different molar ratios of citric acid (0-40 mol%) and added them. This minimizes the undesirable hydrolysis effect of free carboxylic groups on starch chains. The results demonstrated that the migration of plasticizers in TPS/PVA blends decreased by up to 70 % when the citric acid content increased. This reduction was attributed to the higher molecular weight (the majority in the range 764-2060 Da) and the 3D structure of the oligomers compared to using raw glycerol. Furthermore, the films exhibited a 150 % increase in Young's modulus and tensile strength without a reduction in elongation at break, while maintaining a high gel content, due to a moderate crosslinking.


Plasticizers , Polyvinyl Alcohol , Polyvinyl Alcohol/chemistry , Plasticizers/chemistry , Glycerol/chemistry , Polyesters , Citric Acid/chemistry , Starch/chemistry
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