Degradable Polymeric Materials Research Articles

Efficient synthesis of polycarbonate ether polyol via copolymerization of CO2 and 1,2-butylene oxide over a layered Zn-Co double metal cyanide catalyst.

Polycarbonate ether polyol synthesized by the copolymerization of carbon dioxide (CO2) and epoxides is a promising technology for chemically fixing CO2 and manufacturing degradable polymeric materials. However, research on the copolymerization of CO2 and 1,2-butylene oxide (BO) to produce polycarbonate ether polyol is relatively scarce. Herein, we employed layered Zn-Co double metal cyanide (L-DMC) as a catalyst for the copolymerization of CO2 and BO to obtain polycarbonate ether polyol. Under optimized conditions, the L-DMC-mediated copolymerization of CO2 and BO displays excellent activity (catalytic productivity up to 1500 g polymer per g catalyst) and a high CO2 incorporation fraction in polycarbonate ether polyol rate of 35.5%. In situ FTIR spectroscopy experiments showed a short induction period (10 min) in polymerization and competition between the synthesized polycarbonate ether polyol and butylene carbonate (BC). The properties of easy preparation, stability, and excellent catalytic performance of L-DMC suggest that it may be a promising candidate for large-scale production of CO2-BO-based polymers.

Electrospun Membrane Fabrication in Assisting Tissues Healing

The arrangement of fibers into three-dimensional (3D) complex structure is constructing a sheet of membrane, depending on the fabrication technique. The fiber mats and scaffolds have been used in various applications including tissue engineering which involve the integration of cells and tissues within the pores between the fibers. There are several techniques that have been opted to produce specifically nanofibers as its efficacy in tissue healing is prominent compared to microfibers. Among the fabrication techniques (drawing, template synthesis, temperature-induced phase separation, molecular self-assembly, and electrospinning), electrospinning method has drawn attention due to their easy handling, inexpensive, and ability for membrane scale-up with the production of fibers ranging from few nanometers to several microns. Researchers have employed a variety of electrospinning methods, including blended/co-electrospinning, emulsion, coaxial, side-by-side, and triaxial electrospinning. In electrospinning smooth formation of nanofibers for tissue healing with less appearance of spray and beads, several parameters such as humidity, temperature, voltage, flow rate, viscosity, concentration, molecular weight, surface tension, conductivity, and solvent volatile need to be tailored. The morphology of nanofibers formation should support the size and structure of the surrounded cells and tissues. Besides, the types of degradable polymeric materials also play a role in the formation of stable nanofibers. This review paper aimed to provide information on the techniques to produce nanofibers, intended to the basic exploration of electrospinning.

Surface Biofunctionalization of Gadolinium Phosphate Nanobunches for Boosting Osteogenesis/Chondrogenesis Differentiation.

In order to achieve smart biomedical micro/nanomaterials, promote interaction with biomolecules, improve osteogenic/chondrogenic differentiation, exhibit better dispersion in bone implants and ultimately maximize functionality, we innovatively and successfully designed and synthesized polymer PBLG-modified GdPO4·H2O nanobunches by hydroxylation, silylation and glutamylation processes. The effects of different feeding ratios on the surface coating of GdPO4·H2O with Si-OH, the grafting γ-aminopropyltriethoxysilane (APS) and the in situ ring-opening polymerization reaction of poly(g-benzyl-L-glutamate) (PBLG) were investigated, and the physical and chemical properties were characterized in detail. When GdPO4·H2O@SiO2-APS:NCA = 4:1, the PBLG-g-GdPO4·H2O grafting rate was 5.93%, with good stability and dispersion in degradable polymeric materials. However, the MRI imaging signal was sequentially weakened as the modification process proceeded. Despite this, the biological effects had surprising findings. All the modifiers at appropriate concentrations were biocompatible and biologically active and the biomacromolecules of COL I and COL II in particular were expressed at least 3 times higher in GdPO4·H2O@SiO2 compared to the PLGA. This indicates that the appropriate surface modification and functionalization of gadolinium-containing micro/nanomaterials can promote interaction with cells and encourage bone regeneration by regulating biomacromolecules and can be used in the field of biomedical materials.

Mechanically Strong and Tough Poly(urea-urethane) Thermosets Capable of Being Degraded under Mild Condition.

The development of degradable polymeric materials such as degradable polyurethane or polyurea has been much highlighted for resource conservation and environmental protection. Herein, a facile strategy of constructing mechanically strong and tough poly(urea-urethane) (PUU) thermosets that can be degraded under mild conditions by using triple boron-urethane bonds (TBUB) as cross-linkers is demonstrated. By tailoring the molecular weight of the soft segment of the prepolymers, the mechanical performance can be finely controlled. Based on the cross-linking of TBUB units and hydrogen-binding interactions between TBUB linkages, the as-prepared PUU thermosets have excellent mechanical strength of ≈40.2MPa and toughness of ≈304.9MJm-3 . Typically, the PBUU900 strip can lift a barbell with 60000 times its own weight, showing excellent load-bearing capacity. Meanwhile, owing to the covalent cross-linking of TBUB units, all the PUU thermosets show initial decomposition temperatures over 290°C, which are comparable to those of the traditional thermosets. Moreover, the TBUB cross-linked PUU thermosets can be easily degraded in a mild acid solution. The small pieces of the PBUU sample can be fully decomposed in 1m HCl/THF solution for 3.5h at room temperature.

In Vivo Degradation Studies of PGA-PLA Block Copolymer and Their Histochemical Analysis for Spinal-Fixing Application.

Polylactic acid (PLA) and polyglycolic acid (PGA) are well-known medical-implant materials. Under the consideration of the limitations of degradable polymeric materials, such as weak mechanical strength and by-product release through the biodegradation process under in vivo environments, PLA–PGA block copolymer is one of the effective alternative implant materials in the clinical field. In our previous study, two types of extremely effective PGA–PLA copolymers (multi/tri-block PGA–PLA copolymers) were synthesized. These synthesized block copolymers could overcome aforementioned issues and also showed good biocompatibility. In this study, the PGA–PLA block copolymers with large molecular weight were synthesized under the same chemical scheme, and their bio durability was confirmed through the in vivo degradation behavior and histochemical analyses (by hematoxylin and eosin and immune staining) in comparison with commercial PLGA random copolymer (medical grade). Specimens for the degradation test were investigated by SEM and X-ray diffractometer (XRD). As a result, the synthesized PGA–PLA block copolymer showed good biocompatibility and had a controlled biodegrading rate, making it suitable for use in resorbable spinal-fixation materials.

Evaluation of the biodegradation of polymeric materials in the freshwater environment—An attempt to prolong and accelerate the biodegradation experiment

Available international standards describing the biodegradability testing in freshwater were designed primarily for chemicals that undergo relatively fast biodegradation (in the order of days). The current study was undertaken to verify their applicability for testing of slowly degradable polymeric materials, and also describes an attempt to accelerate the biodegradation testing by the increase of the incubation temperature from 25 °C to 37 °C. The polymers tested include TÜV AUSTRIA Belgium certified polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polybutylene adipate-terephthalate, and polylactic acid blend (PBAT/PLA), and an experimental polyester network (ICL-PN). The biodegradation rates of the given polymers at the two temperatures were examined by carbon dioxide evolution and additional information was collected from microscopy observations of the materials and the investigation of the microbial community composition and dynamics. Testing was done at two independent laboratories and the results were compared. It was found that at 25 °C the testing environment was relatively stable, and the incubation can be prolonged up to 12 months. At 37 °C however some undesirable phenomena like higher variability between replicates and laboratories, fungi development, and biomass autolysis were observed. Moreover, the increase in temperature did not accelerate the biodegradation process. Based on the comparison of results from the two laboratories, recommendations for the experimental procedure are given.

Development of oxidatively degradable polymeric materials that can be easily recycled and reused, reducing negative environmental impacts.

Polymers are useful and increasingly prolific and their improper disposal is a growing problem. Diacylhydrazine can be incorporated into polymers to enhance thermal and chemical stability and may also make them oxidatively degradable, which means they can be easily and safely disposed of after use, with no environmental implications. Professor Nobuhiro Kihara, Department of Chemistry, Kanagawa University, Japan, recognised the need for a polymer that has a degradation reaction initiated by artificial stimuli, which led him to study oxidatively degradable polymers. Using diacylhydrazine, he and his team have developed a polymer that boasts attractive properties and numerous applications and benefits. The polymer maintains high strength, is weather resistant and resistant to heat, water, acid and sunlight yet is rapidly degradable when it is time to start the degradation process. This means that it can be easily and conveniently disposed of after use. It can be used in plastic, adhesive or paint and the composite materials can be separated and recycled or reused after use. The expectation is that oxidative degradation will reduce the load for the disposal of plastic and there are further opportunities to explore as there is potential for the use of various oxidant-induced degradation reactions in the design of degradable polymers, as well as artificial stimuli other than oxidation, for example electric current, to promote degradation. Kihara and the team have developed an oxidatively degradable epoxy resin that can be used as an adhesive and an oxidatively degradable SAP (superabsorbent polymer).

A sustainable approach for the synthesis of recyclable cyclic CO2-based polycarbonates.

It is highly desirable to reduce the environmental pollution related to the disposal of end-of-life plastics. Polycarbonates derived from the copolymerization of CO2 and epoxides have attracted much attention since they can enable CO2-fixation and furnish biorenewable and degradable polymeric materials. So far, only linear CO2-based polycarbonates have been reported and typically degraded to cyclic carbonates. Here we synthesize a homogeneous dinuclear methyl zinc catalyst ((BDI-ZnMe)2, 1) to rapidly copolymerize meso-CHO and CO2 into poly(cyclohexene carbonate) (PCHC) with an unprecedentedly cyclic structure. Moreover, in the presence of trace amounts of water, a heterogeneous multi-nuclear zinc catalyst ((BDI-(ZnMe2·xH2O))n, 2) is prepared and shows up to 99% selectivity towards the degradation of PCHC back to meso-CHO and CO2. This strategy not only achieves the first case of cyclic CO2-based polycarbonate but also realizes the complete chemical recycling of PCHC back to its monomers, representing closed-loop recycling of CO2-based polycarbonates.

Plant Cellulose Nanofiber-Derived Structural Material with High-Density Reversible Interaction Networks for Plastic Substitute.

Ubiquitous petrochemical-based plastics pose a potential threat to ecosystems. In response, bioderived and degradable polymeric materials are being developed, but their mechanical and thermal properties cannot compete with those of existing petrochemical-based plastics, especially those used as structural materials. Herein, we report a biodegradable plant cellulose nanofiber (CNF)-derived polymeric structural material with high-density reversible interaction networks between nanofibers, exhibiting mechanical and thermal properties better than those of existing petrochemical-based plastics. This all-green material has substantially improved flexural strength (∼300 MPa) and modulus (∼16 GPa) compared with those of existing petrochemical-based plastics. Its average thermal expansion coefficient is only 7 × 10-6 K-1, which is more than 10 times lower than those of petrochemical-based plastics, indicating its dimension is almost unchanged when heated, and thus, it has a thermal dimensional stability that is better than those of plastics. As a fully bioderived and degradable material, the all-green material offers a more sustainable high-performance alternative to petrochemical-based plastics.

Pinwheel-Shaped Tetranuclear Organoboron Catalysts for Perfectly Alternating Copolymerization of CO2 and Epichlorohydrin.

The copolymerization of carbon dioxide (CO2) and epoxides to produce aliphatic polycarbonates is a burgeoning technology for the large-scale utilization of CO2 and degradable polymeric materials. Even with the wealth of advancements achieved over the past 50 years on this green technology, many challenges remain, including the use of metal-containing catalysts for polymerization, the removal of the chromatic metal residue after polymerization, and the limited practicable epoxides, especially for those containing electron-withdrawing groups. Herein, we provide kinds of pinwheel-shaped tetranuclear organoboron catalysts for epichlorohydrin/CO2 copolymerization with >99% polymer selectivity and quantitative CO2 uptake (>99% carbonate linkages) under mild conditions (25-40 °C, 25 bar of CO2). The produced poly(chloropropylene carbonate) has the highest molecular weight of 36.5 kg/mol and glass transition temperature of 45.4 °C reported to date. The energy difference (ΔEa = 60.7 kJ/mol) between the cyclic carbonate and polycarbonate sheds light on the robust performance of our metal-free catalyst. Control experiments and density functional theory (DFT) calculations revealed a cyclically sequential copolymerization mechanism. The metal-free feature, high catalytic performance under mild conditions, and no trouble with chromaticity for the produced polymers imply that our catalysts are practical candidates to advance the CO2-based polycarbonates.

In Vitro and In Vivo Biosafety Analysis of Resorbable Polyglycolic Acid-Polylactic Acid Block Copolymer Composites for Spinal Fixation.

Herein, spinal fixation implants were constructed using degradable polymeric materials such as PGA–PLA block copolymers (poly(glycolic acid-b-lactic acid)). These materials were reinforced by blending with HA-g-PLA (hydroxyapatite-graft-poly lactic acid) and PGA fiber before being tested to confirm its biocompatibility via in vitro (MTT assay) and in vivo animal experiments (i.e., skin sensitization, intradermal intracutaneous reaction, and in vivo degradation tests). Every specimen exhibited suitable biocompatibility and biodegradability for use as resorbable spinal fixation materials.

(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.

Crystal Engineering Construction of Caffeic Acid Derivatives with Potential Applications in Pharmaceuticals and Degradable Polymeric Materials.

Natural products are precious feedstock in drug discovery and sustainable materials. This work using crystal engineering strategy, visible light, and solvent-free cycloaddition successfully constructed two caffeic acid derivatives, rel-(1R,2R,3S,4S)-2,4-bis(3,4-dihydroxyphenyl)cyclobutane-1,3-dicarboxylate and rel-(1R,2R,3S,4S)-2,4-bis(3,4-dihydroxyphenyl)cyclobutane-1,3-dicarboxylic acid. Because of the multiple stereocenters, it is challenging to prepare those compounds using traditional organic synthesis methods. The crystal engineering Hirshfeld surface analysis and 2D intermolecular interaction fingerprints were applied to synthetic route design. The light resources used in this work was visible LED or free, clean, and renewable sunlight. The evidence suggested that pure stereoisomer was obtained demonstrating the stereospecificity and efficiency of the topochemical cycloaddition reaction. The derivatives exhibited free radical scavenging and antioxidant biological activities, as well as the potential inhibitory activity of fatty acid binding proteins. One of the derivatives is the precursor of the natural product Shimobashiric acid C which paves the way for the total synthesis and further study of Shimobashiric acid C. In addition, the derivatives possess photodegradability at a specific wavelength, which is very attractive for "green" degradable polymeric materials.

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.

(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.

(Bio)degradable polymeric materials for a sustainable future – part 1. Organic recycling of PLA/PBAT blends in the form of prototype packages with long shelf-life

Prediction studies of advanced (bio)degradable polymeric materials are crucial when their potential applications as compostable products with long shelf-life is considered for today’s market. The aim of this study was to determine the effect of the polylactide (PLA) content in the blends of PLA and poly(butylene adipate-co-terephthalate) (PBAT); specifically how the material’s thickness corresponded to changes that occurred in products during the degradation process. Additionally, the influence of talc on the degradation profile of all samples in all environments was investigated. It was found that, differences in the degradation rate of materials tested with a similar content of the PLA component could be caused by differences in their thickness, the presence of commercial additives used during processing or a combination of both. The obtained results indicated that the presence of talc may interfere with materials behavior towards water and consequently alter their degradation profile.

Polymer-Based Nanomaterials and Applications for Vaccines and Drugs.

Nanotechnology plays a significant role in drug development. As carriers, polymeric nanoparticles can deliver vaccine antigens, proteins, and drugs to the desired site of action. Polymeric nanoparticles with lower cytotoxicity can protect the delivered antigens or drugs from degradation under unfavorable conditions via a mucosal administration route; further, the uptake of nanoparticles by antigen-presenting cells can increase and induce potent immune responses. Additionally, nanomaterials are widely used in vaccine delivery systems because nanomaterials can make the vaccine antigen long-acting. This review focuses on some biodegradable polymer materials such as natural polymeric nanomaterials, chemically synthesized polymer materials, and biosynthesized polymeric materials, and points out the advantages and the direction of research on degradable polymeric materials. The application and future perspectives of polymeric materials as delivery carriers and vaccine adjuvants in the field of drugs and vaccines are presented. With the increase of knowledge and fundamental understandings of polymer-based nanomaterials, means of integrating some other attractive properties, such as slow release, target delivery, and alternative administration methods and delivery pathways are feasible. Polymer-based nanomaterials have great potential for the development of novel vaccines and drug systems for certain needs, including single-dose and needle-free deliveries of vaccine antigens and drugs in the future.

Current Status of Methods Used In Degradation of Polymers: A Review

Degradation of different polymers now a day is the most crucial thing to carry out. It possesses threats to human health as well as to the environment. Different polymers like PVA, PVC, and PP with high density and low density are one of the most consumed by population and also their degradation is a bit difficult. For this many people have started working on effective methods of degradation of these polymers. This can be done by thermal degradation and pyrolysis which requires high temperature, bio degradation using starch, bacteria etc and photo degradation. Traditional gravimetric and respirometric techniques are the methods currently used in testing. They fit readily for degradable polymeric materials usually. Also they are well suited for biodegradable components with polymer blends. But the recent polymer generation is comparatively resistant to bio degradation of polymers hence they cannot be used here. The polymer matrices are readily present in the plasticizers boosting the strength of polymeric material hence in addition; there is the mechanism of degradation. The information on various methods discussed in this review is planned to illustrate a best fit of methods for those who are interested in testing the degradation of polymers under different environmental conditions and selection of appropriate technique for specific combination of mixture of polymer and catalysts which helps to degrade the polymeric material.

Current Status of Methods Used In Degradation of Polymers: A Review

Degradation of different polymers now a day is the most crucial thing to carry out. It possesses threats to human health as well as to the environment. Different polymers like PVA, PVC, and PP with high density and low density are one of the most consumed by population and also their degradation is a bit difficult. For this many people have started working on effective methods of degradation of these polymers. This can be done by thermal degradation and pyrolysis which requires high temperature, bio degradation using starch, bacteria etc and photo degradation. Traditional gravimetric and respirometric techniques are the methods currently used in testing. They fit readily for degradable polymeric materials usually. Also they are well suited for biodegradable components with polymer blends. But the recent polymer generation is comparatively resistant to bio degradation of polymers hence they cannot be used here. The polymer matrices are readily present in the plasticizers boosting the strength of polymeric material hence in addition; there is the mechanism of degradation. The information on various methods discussed in this review is planned to illustrate a best fit of methods for those who are interested in testing the degradation of polymers under different environmental conditions and selection of appropriate technique for specific combination of mixture of polymer and catalysts which helps to degrade the polymeric material.

Lipogels responsive to near-infrared light for the triggered release of therapeutic agents

Hydrogels composed of fibrin embedding nanoparticles responsive to near infrared (NIR) energy and thermosensitive liposomes loaded with doxorubicin hydrochloride (DOX), were prepared by in situ polymerization. NIR-light irradiation of these constructs, referred to as "NIR responsive lipogels", results in the controlled release of DOX to the surrounding medium. This technology may use fully degradable components and can preserve the bioactivity of liposomal cargo after remote triggering to finely regulate the dose and bioavailability of delivered payloads. NIR responsive lipogels technology overcomes the limitations of drug release systems based on the combination of liposomes and degradable polymeric materials, which in many cases lead to insufficient release at therapy onset or to overdose during high degradation period.