Mechanical and Rheological Evaluation of Polyester-Based Composites Containing Biochar.

The use of biodegradable polymers as matrices in composites gives a wide range of applications, especially in niche areas. The assessment of the effect of the filler content on the change of mechanical properties makes it possible to optimize the composition for specific needs. Biochar was used as a filler in the studied composites with two different biodegradable blends as a matrix. Poly(1,4-butylene adipate-co-1,4-butylene terephthalate)/polylactide/biochar (PBAT/PLA/BC) and polylactide/poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate]/biochar (PLA/P(3HB-co-4HB)/BC) composites with 0, 10, 15, 20 and 30 wt% of biochar underwent mechanical tests. The test results revealed a change in the properties of the composites related to the filler content. The results of the tensile test showed that increasing the biochar content increased the tensile modulus values by up to 100% for composites with 30 wt% of biochar, compared to unfilled matrices, and decreased the elongation associated with the breaking of PBAT/PLA and PLA/P(3HB-co-4HB) matrix composites. The elongation values at break of PBAT/PLA and PLA/(3HB-co-4HB) composites with 30 wt% biochar were reduced by 50% and 65%, respectively, compared to the unfilled matrices. PLA/P(3HB-co-4HB) matrix composites, in contrast to PBAT/PLA/BC, showed a decrease in tensile strength with the increases in filler content from 35.6 MPa for unfilled matrix to 27.1 MPa for PLA/P(3HB-co-4HB)/BC30 composites. An increase in filler content increased the brittleness of the composites regardless of the matrix used, as determined under the Charpy impact-test. This phenomenon was observed for all tested PLA/P(3HB-co-4HB) composites, for which the impact strength decreased from 4.47 kJ/m2 for the matrix to 1.61 kJ/m2 for the composite containing 30 wt% biochar. PBAT/PLA-based composites with 10 wt% of biochar showed slightly lower impact strength compared to the unfilled matrix, but composites with 30 wt% biochar showed 30% lower impact strength than PBAT/PLA. The complex viscosity value increased with increased filler content. For all composites tested on both polyester matrices, the viscosity decreased with increasing angular frequency.

Towards scalable and degradable bioplastic films from Moringa oleifera gum/poly(vinyl alcohol) as packaging material.

The use of plant gum-based biodegradable bioplastic films as a packaging material is limited due to their poor physicochemical properties. However, combining plant gum with synthetic degradable polymer and some additives can improve these properties. Keeping in view, the present study aimed to synthesize a series of bioplastic films using Moringa oleifera gum, polyvinyl alcohol, glycerol, and citric acid via thermal treatment followed by a solution casting method. The films were characterized using analytical techniques such as FTIR, XRD, SEM, AFM, TGA, and DSC. The study examined properties such as water sensitivity, gas barrier attributes, tensile strength, the shelf life of food, and biodegradability. The films containing higher citric acid amounts showed appreciable %elongation without compromising tensile strength, good oxygen barrier properties, and biodegradation rates (>95%). Varying the amounts of glycerol and citric acid in the films broadened their physicochemical properties ranging from hydrophilicity to hydrophobicity and rigidity to flexibility. As all the films were synthesized using economical and environmentally safe materials, and showed better physicochemical and barrier properties, this study suggests that these bioplastic films can prove to be a potential alternative for various packaging applications.

Oligopeptide-based molecular labelling of (bio)degradable polyester biomaterials.

Nowadays, a very important motivation for the development of new functional materials for medical purposes is not only their performance but also whether they are environmentally friendly. In recent years, there has been a growing interest in the possibility of labelling (bio)degradable polymers, in particular those intended for specific applications, especially in the medical sector, and the potential of information storage in such polymers, making it possible, for example, to track the ultimate environmental fate of plastics. This article presents a straightforward green approach that combines both aspects using an oligopeptide, which is an integral part of polymer material, to store binary information in a physical mixture of polymer and oligopeptide. In the proposed procedure the year of production of polymer films made of poly(l-lactide) (PLLA) and a blend of poly(1,4-butylene adipate-co-1,4-butylene terephthalate) and polylactide (PBAT/PLA) were encoded as the sequence of the appropriate amino acids in the oligopeptide (PEP) added to these polymers. The decoding of the recorded information was carried out using mass spectrometry technique as a new method of decoding, which enabled the successful retrieval and reading of the stored information. Furthermore, the properties of labelled (bio)degradable polymer films and stability during biodegradation of PLLA/PEP film under industrial composting conditions have been investigated. The labelled films exhibited good oligopeptide stability, allowing the recorded information to be retrieved from a green polymer/oligopeptide system before and after biodegradation. The MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide assay) study of the PLLA and PLLA/PBAT using the MRC-5 mammalian fibroblasts was presented for the first time.

Polymer-Drug Anti-Thrombogenic and Hemocompatible Coatings as Surface Modifications.

Since the 1960s, efforts have been made to develop new technologies to eliminate the risk of thrombosis in medical devices that come into contact with blood. Preventing thrombosis resulting from the contact of a medical device, such as an implant, with blood is a challenge due to the high mortality rate of patients and the high cost of medical care. To this end, various types of biomaterials coated with polymer-drug layers are being designed to reduce their thrombogenicity and improve their hemocompatibility. This review presents the latest developments in the use of polymer-drug systems to produce anti-thrombogenic surfaces in medical devices in contact with blood, such as stents, catheters, blood pumps, heart valves, artificial lungs, blood vessels, blood oxygenators, and various types of tubing (such as for hemodialysis) as well as microfluidic devices. This paper presents research directions and potential clinical applications, emphasizing the importance of continued progress and innovation in the field.

Biosynthesis and Biodegradation-Eco-Concept for Polymer Materials.

Polymers have become essential for various aspects of modern life, including packaging, transportation, and electronics [...].

Naphthalene Phthalimide Derivatives as Model Compounds for Electrochromic Materials.

Electrochromism of organic compounds is a well-known phenomenon; however, nowadays, most research is focused on anodic coloring materials. Development of efficient, cathodic electrochromic materials is challenging due to the worse stability of electron accepting materials compared with electron donating ones. Nevertheless, designing stable cathodic coloring organic materials is highly desired-among other reasons-to increase the coloration performance. Hence, four phthalimide derivatives named 1,5-PhDI, 1,4-PhDI, 2,6-PhDI and 3,3'-PhDI were synthesized and analyzed in depth. In all cases, two imide groups were connected via naphthalene (1,5-PhDI, 1,4-PhDI, 2,6-PhDI) or 3,3'-dimethylnaphtidin (3,3'-PhDI) bridge. To observe the effect of chemical structure on physicochemical properties, various positions of imide bond were considered, namely, 1,5- 1,4- and 2,6-. Additionally, a compound with the pyromellitic diimide unit capped with two 1-naphtalene substituents was obtained. All compounds were studied in terms of their thermal behavior, using differential calorimetry (DSC) and thermogravimetric analysis (TGA). Moreover, electrochemical (CV, DPV) and spectroelectrochemical (UV-Vis and EPR) analyses were performed to evaluate the obtained materials in terms of their application as cathodic electrochromic materials. All obtained materials undergo reversible electrochemical reduction which leads to changes in their optical properties. In the case of imide derivatives, absorption bands related to both reduced and neutral forms are located in the UV region. However, importantly, the introduction of the 3,3'-dimethylnaphtidine bridge leads to a noticeable bathochromic shift of the reduced form absorption band of 3,3'-PhDI. This indicates that optimization of the phthalimide structure allows us to obtain stable, cathodic electrochromic materials.

Designing of Drug Delivery Systems to Improve the Antimicrobial Efficacy in the Periodontal Pocket Based on Biodegradable Polyesters.

Delivery systems for biologically active substances such as proanthocyanidins (PCANs), produced in the form of electrospun nonwoven through the electrospinning method, were designed using a polymeric blend of poly(L-lactide-co-glycolide) (PLGA)and poly[(R,S)-3-hydroxybutyrate] ((R,S)-PHB). The studies involved the structural and thermal characteristics of the developed electrospun three-dimensional fibre matrices unloaded and loaded with PCANs. In the next step, the hydrolytic degradation tests of these systems were performed. The release profile of PCANs from the electrospun nonwoven was determined with the aid of UV-VIS spectroscopy. Approximately 30% of the PCANs were released from the tested electrospun nonwoven during the initial 15-20 days of incubation. The chemical structure of water-soluble oligomers that were formed after the hydrolytic degradation of the developed delivery system was identified through electrospray ionization mass spectrometry. Oligomers of lactic acid and OLAGA oligocopolyester, as well as oligo-3-hydroxybutyrate terminated with hydroxyl and carboxyl end groups, were recognized as degradation products released into the water during the incubation time. It was also demonstrated that variations in the degradation rate of individual mat components influenced the degradation pattern and the number of formed oligomers. The obtained results suggest that the incorporation of proanthocyanidins into the system slowed down the hydrolytic degradation process of the poly(L-lactide-co-glycolide)/poly[(R,S)-3-hydroxybutyrate] three-dimensional fibre matrix. In addition, in vitro cytotoxicity and antimicrobial studies advocate the use of PCANs for biomedical applications with promising antimicrobial activity.

Applications of Novel Biodegradable Polymeric Materials.

Commonly used traditional polymeric materials have many advantages, although their resistance to biological agents causes a negative impact on the environment [...].

Co-Delivery of 8-Hydroxyquinoline Glycoconjugates and Doxorubicin by Supramolecular Hydrogel Based on α-Cyclodextrin and pH-Responsive Micelles for Enhanced Tumor Treatment.

The sustained release of multiple anti-cancer drugs using a single delivery carrier to achieve a synergistic antitumor effect remains challenging in biomaterials and pharmaceutics science. In this study, a supramolecular hydrogel based on the host-guest complexes between pH-responsive micelle derived poly(ethylene glycol) chains and α-cyclodextrin was designed for codelivery of two kinds of anti-cancer agents, hydrophilic 8-hydroxyquinoline glycoconjugate and hydrophobic doxorubicin. The host-guest interactions were characterized using X-ray diffraction and differential scanning calorimetry techniques. The resultant supramolecular hydrogel showed thixotropic properties, which are advantageous to drug delivery systems. In vitro release studies revealed that the supramolecular hydrogel exhibited faster drug release profiles in acidic conditions. The MTT assay demonstrated a synergistic cancer cell proliferation inhibition of DOX/8HQ-Glu mixture. In vitro cytotoxicity studies indicated excellent biocompatibility of the supramolecular hydrogel matrix, whereas the DOX/8HQ-Glu-loaded supramolecular hydrogel showed a sustained inhibition efficacy against cancer cells. The codelivery of hydrophobic anti-cancer drugs and hydrophilic anti-cancer drug glycoconjugates via a pH-responsive supramolecular hydrogel opens up new possibilities for the development of an effective cancer treatment based on the tumor-specific Warburg effect.

Functionalized Moringa oleifera Gum as pH-Responsive Nanogel for Doxorubicin Delivery: Synthesis, Kinetic Modelling and In Vitro Cytotoxicity Study

Environment-responsive-cum-site-specific delivery of therapeutic drugs into tumor cells is a foremost challenge for chemotherapy. In the present work, Moringa oleifera gum-based pH-responsive nanogel (MOGN) was functionalized as a doxorubicin (DOX) carrier. It was synthesized via free radical polymerization through the γ-irradiation method using acrylamide and N,N'-MBA followed by hydrolysis, sonication, and ultracentrifugation. The swelling behavior of MOGN as a function of pH was assessed using a gravimetric method that revealed its superabsorbent nature (365.0 g/g). Furthermore, MOGN showed a very high loading efficiency (98.35 %L) of DOX by MOGN. In vitro release studies revealed that DOX release from DOX-loaded MOGN was 91.92% at pH 5.5 and 12.18% at 7.4 pH, thus favorable to the tumor environment. The drug release from nanogel followed Korsmeyer-Peppas model at pH 5.5 and 6.8 and the Higuchi model at pH 7.4. Later, the efficient DOX release at the tumor site was also investigated by cytotoxicity study using Rhabdomyosarcoma cells. Thus, the synthesized nanogel having high drug loading capacity and excellent pH-triggered disintegration and DOX release performance in a simulated tumor environment could be a promising candidate drug delivery system for the targeted and controlled release of anticancer drugs.

Electrospun Nisin-Loaded Poly(ε-caprolactone)-Based Active Food Packaging.

Packaging for fresh fruits and vegetables with additional properties such as inhibition of pathogens grown can reduce food waste. With its biodegradability, poly(ε-caprolactone) (PCL) is a good candidate for packaging material, especially in the form of an electrospun membrane. The preparation of nonwoven fabric of PCL loaded with food additive, antimicrobial nisin makes them an active packaging with antispoilage properties. During the investigation of the nonwoven fabric mats, different concentrations of nisin were obtained from the solution of PCL via the electrospinning technique. The obtained active porous PCL loaded with varying concentrations of nisin inhibited the growth of Staphylococcus aureus and Escherichia coli. Packages made of PCL and PCL/nisin fibrous mats demonstrated a prolongation of the fruits' freshness, improving their shelf life and, consequently, their safety.

Nematic-to-Isotropic Phase Transition in Poly(L-Lactide) with Addition of Cyclodextrin during Abiotic Degradation Study.

Poly(L-lactide) is capable of self-assembly into a nematic mesophase under the influence of temperature and mechanical stresses. Therefore, subsequent poly(L-lactide) films were obtained and characterized, showing nematic liquid crystal properties both before and after degradation. Herein, we present that, by introducing ß-cyclodextrin into the polymer matrix, it is possible to obtain a chiral nematic mesophase during pressing, regardless of temperature and time. The obtained poly(L-lactide) films exhibiting liquid crystal properties were subjected to degradation tests and the influence of degradation on these properties was determined. Thermotropic phase behavior was investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The degradation process demonstrated an influence on the liquid crystal properties of pressed polymer films. The colored planar texture of the chiral nematic mesophase, which was not observed prior to degradation in films without the addition of ß-cyclodextrin, appeared after incubation in water as a result of the entrapment of degradation products in the polymer matrix. These unusual tailor-made properties, obtained in liquid crystals in (bio)degradable polymers using a simple method, demonstrate the potential for advanced photonic applications.

Poly(l-Lactide) Liquid Crystals with Tailor-Made Properties Toward a Specific Nematic Mesophase Texture.

This paper presents the liquid crystal (LC) properties of poly(l-lactide) (PLLA). Mesophase behavior is investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The performed analyses confirm that pressed PLLA films exhibit the unique capability of self-assembling into a nematic mesophase under the influence of mechanical pressure, temperature, and time. It was originally demonstrated that the chiral nematic mesophase can be obtained by introducing fine powders into the polymer. Based on the research conducted, it was proved that the pressed PLLA films have a chiral nematic mesophase with a nematic-to-isotropic phase transition and a large mesophase stability range overlapping the temperature of the human body, which can persist for years at ambient temperature. The obtained films show tailor-made properties toward a nematic mesophase with a specific texture, including colored planar texture of the chiral nematic mesophase and blue-phase (BP) LC texture. The BP, described for the first time in plain PLLA, occurred over a wider than usual temperature range of stability between isotropic and chiral nematic thermotropic phases (ΔT ≈ 9 °C), which is an advantage of the obtained polymer material, in addition to ease of preparation. This opens up new prospects for advanced photonic green applications.

The Effect of Alkyl Substitution of Novel Imines on Their Supramolecular Organization, towards Photovoltaic Applications.

Three novel conjugated polyazomethines have been obtained by polycondensation of diamines consisting of the diimine system, with either 2,5-bis(octyloxy)terephthalaldehyde or 9-(2-ethylhexyl)carbazole-3,6-dicarboxaldehyde. Partial replacement of bulky solubilizing substituents with the smaller side groups has allowed to investigate the effect of supramolecular organization. All obtained compounds have been subsequently identified using the NMR and FTIR spectroscopies and characterized by the thermogravimetric analysis, differential scanning calorimetry, cyclic voltammetry, UV-Vis spectroscopy, and X-ray diffraction. Investigated polymers have shown a good thermal stability and high glass transition temperatures. X-ray measurements have proven that partial replacement of octyloxy side chains with smaller methoxy groups induced a better planarization of macromolecule. Such modification has tuned the LUMO level of this molecule and caused a bathochromic shift of the lowest energy absorption band. On the contrary, imines consisting of N-ethylhexyl substituted carbazole units have not been so clearly affected by alkyl chain length modification. Photovoltaic activity of imines (acting as a donor) in bulk-heterojunction systems has been observed for almost all studied compounds, blended with the fullerene derivative (PCBM) in various weight ratios.

(Bio)Degradable Polymeric Materials for Sustainable Future-Part 3: Degradation Studies of the PHA/Wood Flour-Based Composites and Preliminary Tests of Antimicrobial Activity.

The need for a cost reduction of the materials derived from (bio)degradable polymers forces research development into the formation of biocomposites with cheaper fillers. As additives can be made using the post-consumer wood, generated during wood products processing, re-use of recycled waste materials in the production of biocomposites can be an environmentally friendly way to minimalize and/or utilize the amount of the solid waste. Also, bioactive materials, which possess small amounts of antimicrobial additives belong to a very attractive packaging industry solution. This paper presents a study into the biodegradation, under laboratory composting conditions, of the composites that consist of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate)] and wood flour as a polymer matrix and natural filler, respectively. Thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy were used to evaluate the degradation progress of the obtained composites with different amounts of wood flour. The degradation products were characterized by multistage electrospray ionization mass spectrometry. Also, preliminary tests of the antimicrobial activity of selected materials with the addition of nisin were performed. The obtained results suggest that the different amount of filler has a significant influence on the degradation profile.

Three-Dimensional Printed PLA and PLA/PHA Dumbbell-Shaped Specimens: Material Defects and Their Impact on Degradation Behavior.

The use of (bio)degradable polymers, especially in medical applications, requires a proper understanding of their properties and behavior in various environments. Structural elements made of such polymers may be exposed to changing environmental conditions, which may cause defects. That is why it is so important to determine the effect of processing conditions on polymer properties and also their subsequent behavior during degradation. This paper presents original research on a specimen's damage during 70 days of hydrolytic degradation. During a standard hydrolytic degradation study of polylactide and polylactide/polyhydroxyalkanoate dumbbell-shaped specimens obtained by 3D printing with two different processing build directions, exhibited unexpected shrinkage phenomena in the last degradation series, representing approximately 50% of the length of the specimens irrespective of the printing direction. Therefore, the continuation of previous ex-ante research of advanced polymer materials is presented to identify any possible defects before they arise and to minimize the potential failures of novel polymer products during their use and also during degradation. Studies on the impact of a specific processing method, i.e., processing parameters and conditions, on the properties expressed in molar mass and thermal properties changes of specimens obtained by three-dimensional printing from polyester-based filaments, and in particular on the occurrence of unexpected shrinkage phenomena after post-processing heat treatment, are presented.

Mass Spectrometry Reveals Molecular Structure of Polyhydroxyalkanoates Attained by Bioconversion of Oxidized Polypropylene Waste Fragments.

This study investigated the molecular structure of the polyhydroxyalkanoate (PHA) produced via a microbiological shake flask experiment utilizing oxidized polypropylene (PP) waste as an additional carbon source. The bacterial strain Cupriavidus necator H16 was selected as it is non-pathogenic, genetically stable, robust, and one of the best known producers of PHA. Making use of PHA oligomers, formed by controlled moderate-temperature degradation induced by carboxylate moieties, by examination of both the parent and fragmentation ions, the ESI-MS/MS analysis revealed the 3-hydroxybutyrate and randomly distributed 3-hydroxyvalerate as well as 3-hydroxyhexanoate repeat units. Thus, the bioconversion of PP solid waste to a value-added product such as PHA tert-polymer was demonstrated.

(Bio)degradable Polymeric Materials for Sustainable Future-Part 2: Degradation Studies of P(3HB-co-4HB)/Cork Composites in Different Environments.

The degree of degradation of pure poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] and its composites with cork incubated under industrial and laboratory composting conditions was investigated. The materials were parallelly incubated in distilled water at 70 °C as a reference experiment (abiotic condition). It was demonstrated that addition of the cork into polyester strongly affects the matrix crystallinity. It influences the composite degradation independently on the degradation environment. Moreover, the addition of the cork increases the thermal stability of the obtained composites; this was related to a smaller reduction in molar mass during processing. This phenomenon also had an influence on the composite degradation process. The obtained results suggest that the addition of cork as a natural filler in various mass ratios to the composites enables products with different life expectancies to be obtained.

3D-Printed Polyester-Based Prototypes for Cosmetic Applications-Future Directions at the Forensic Engineering of Advanced Polymeric Materials.

Knowledge of degradation and impairment phenomena of (bio)degradable polymeric materials under operating conditions, and thus the selection of test procedures and prediction of their behavior designates the scope and capabilities as well as possible limitations of both: the preparation of the final product and its durability. The main novelty and objective of this research was to determine the degradation pathways during testing of polylactide and polylactide/polyhydroxyalkanoate materials made with three-dimensional printing and the development of a new strategy for the comprehensive characterization of such complex systems including behavior during waste disposal. Prototype objects were subjected to tests for damage evolution performed under simulating operating conditions. The reference samples and the tested items were characterized by gel permeation chromatography and differential scanning calorimetry to determine changes in material properties. The studies showed that: polyhydroxyalkanoate component during accelerated aging and degradation in environments rich in microorganisms accelerated the degradation of the material; paraffin accelerates polylactide degradation and slows degradation of polyhydroxyalkanoate-based material; under the influence of an environment rich in enzymes, paraffin contamination accelerates biodegradation; under the influence of natural conditions, paraffin contamination slowed degradation; the processing conditions, in particular the printing orientation of individual parts of the container, influenced the material properties in its various regions, affecting the rate of degradation of individual parts.