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Poly(ethylene glycol) (PEG) is a highly biocompatible and water-soluble polymer that is widely utilized for biomedical applications. Unfortunately, the immunogenicity and antigenicity of PEG severely restrict the biomedical efficacy of pegylated therapeutics. As emerging PEG alternatives, biodegradable zwitterionic polymers (ZPs) have attracted significant interest in recent years. Biodegradable ZPs generally are not only water-soluble and immunologically inert, but also possess a range of favorable biomedically relevant properties, without causing long-term side effects for in vivo biomedical applications. This review presents a systematic overview of recent studies on biodegradable ZPs. Their structural designs and synthetic strategies by integrating biodegradable base polymers with zwitterions are addressed. Their applications in the delivery of small molecule drugs (as mono-drugs or multi-drugs) and proteins are highlighted.

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Erosion of biodegradable polymeric excipients, such as polylactic acid (PLA) and polylactic-co-glycolic acid (PLGA), is generally characterized by microbalance for the remaining mass of PLA and/or PLGA and Gel Permeation Chromatography (GPC) for molecular weight (MW) decrease. For polymer erosion studies of intravitreal sustained release brimonidine implants, however, both microbalance and GPC present several challenges. Mass loss measurement by microbalance does not have specificity for excipient polymers and drug substances. Accuracy of the remaining mass by weighing could also be low due to sample mass loss through retrieval-drying steps, especially at later drug release (DR) time points. When measuring the decrease of polymer MW by GPC, trace amounts of polymeric degradants (oligomers and/or monomers) trapped inside the implants during DR tests may not be measurable due to sensitivity limitations of the GPC detector and column MW range. Previous efforts to measure remained PLGA weight of dexamethasone micro-implants using qNMR with external calibration have been performed, however, these measurements do not account for chemical structure changes (i.e. LA to GA ratio changes from time zero) of PLGA implants during drug release tests. Here, a qNMR method with an internal standard was developed to monitor the following changes in micro-implants during drug release tests: 1. The remaining overall PLA/PLGA mass. 2. The remaining lactic acid (LA), glycolic acid (GA) unit and PLGA's lauryl ester end group percentages. 3. The trace content of PLA/PLGA oligomers as degradants retained in the implants. Unlike microbalance analysis, qNMR has both specificity for drug substance, excipient polymer, and accuracy due to minimal implant loss during sample preparation. Compared to the overall PLA/PLGA remaining mass generally monitored in erosion studies, the percentage of remaining LA, GA, and the ester end group provide more information about the microstructure change (such as hydrophobicity) of PLA/PLGA. Additionally, the qNMR method can complement GPC methods by measuring the change of remaining PLA and PLGA oligomer concentrations in brimonidine implants, with tenfold less sample and no MW cutoff. The qNMR method can be used as a sensitive tool for both polymer excipient characterization and kinetics studies of brimonidine implant erosion.

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Plastic pollution is a notable environmental issue, being plastic widespread and characterized by long lifetime. Serious environmental problems are caused by the improper management of plastic end-of-life. In fact, plastic litter is currently detected in any environment. Biodegradable Polymers (BPs) are promising materials if correctly applied and managed at their end of life, to minimize environmental problems. However, poor data on the fate and toxicity of BPs on marine organisms still limit their applicability. In this work we tested the effects of five biodegradable polymers (polybutylene succinate, PBS; polybutylene succinate-co-butylene adipate, PBSA; polycaprolactone, PCL; poly (3-hydroxybutyrates, PHB; polylactic acid, PLA) widely used for several purposes. Adult individuals of the isopod Idotea balthica basteri were fed on these polymers for twenty-seven days by adding biodegradable microplastic polymers (BMPs) to formulated feeds at two concentrations, viz. 0.84 and 8.4 g/kg feed. The plastic fragments affected the mortality rates of the isopods, as well as the expression levels of eighteen genes (tested by Real Time qPCR) involved in stress response and detoxification processes. Our findings confirmed that I. balthica basteri is a convenient model organism to study the response to environmental pollution and emerging contaminants in the aquatic environment, and highlighted the need for the correct use of BMPs.

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BACKGROUND AND AIMS: Neoatherosclerosis is a leading cause of late (>1 year) stent failure following drug-eluting stent implantation. The role of biodegradable (BP) versus durable polymer (DP) drug-eluting stents on long-term occurrence of neoatherosclerosis remains unclear. Superiority of biodegradable against durable polymer current generation thin-strut everolimus-eluting stent (EES) was tested by assessing the frequency of neoatherosclerosis 3 years after primary percutaneous coronary intervention (pPCI) among patients with ST-segment elevation myocardial infarction (STEMI). METHODS: The randomized controlled, multicentre (Japan and Switzerland) CONNECT trial (NCT03440801) randomly (1:1) assigned 239 STEMI patients to pPCI with BP-EES or DP-EES. The primary endpoint was the frequency of neoatherosclerosis assessed by optical coherence tomography (OCT) at 3 years. Neoatherosclerosis was defined as fibroatheroma or fibrocalcific plaque or macrophage accumulation within the neointima. RESULTS: Among 239 STEMI patients randomized, 236 received pPCI with stent implantation (119 BP-EES; 117 DP-EES). A total of 178 patients (75%; 88 in the BP-EES group and 90 in the DP-EES group) underwent OCT assessment at 3 years. Neoatherosclerosis did not differ between the BP-EES (11.4%) and DP-EES (13.3%; odds ratio 0.83, 95% confidence interval 0.33-2.04, p=0.69). There were no differences in the frequency of fibroatheroma (BP-EES 9.1% vs DP-EES 11.1%, p=0.66) or macrophage accumulation (BP-EES 4.5% vs DP-EES 3.3%, p=0.68), and no fibrocalcific neoatherosclerosis was observed. Rates of target lesion failure did not differ between groups (BP-EES 5.9% vs DP-EES 6.0%, p=0.97). CONCLUSIONS: Use of BP-EES for primary PCI in patients presenting with STEMI was not superior to DP-EES regarding frequency of neoatherosclerosis at 3 years.

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Purpose: The primary objective of the conducted research was to develop an urological stent design for the treatment of male ure-thral stenosis. Given the variable loading conditions inside the urethra, the proposed stent should maintain normal tissue kinetics and obstruct the narrowed lumen. The suitable selection for the stent material significantly influences the regeneration and proper remodeling of the urethral tissues. Methods: In this work, the mechanical characteristics of some polymer materials were studied, including: polydi-oxanone (PDO) and poly(L-lactide) (PLLA)/polycaprolactone (PCL) composite. The obtained mechanical properties for static tensile testing of the materials, allowed the determination of such parameters as Young's modulus (E), tensile strength (R m) and yield strength (R e). Subsequently, the design of a urological stent was developed, for which a numerical analysis was carried out to check the behaviour of the stent during varying loads prevailing in the urethra. Result: The research indicated that PDO has better mechanical properties than the proposed PLLA/PCL composite. The numerical analysis results suggested that the developed stent design can be successfully used in the treatment of male urethral stenosis. The obtained stress and strain distributions in the numerical analysis confirm that the PDO material can be used as a material for an urological stent. Conclusions: The biodegradable polymers can be successfully used in urology. Their advantages over solid materials are their physicochemical properties, the ability to manipulate the rate and time of degradation and the easy availability of materials and manufacturing technology.

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Purpose: Titanium alloys are among the most widely used materials in medicine, especially in orthopedics. However, their use requires the application of an appropriate surface modification method to improve their properties. Such methods include anodic oxidation and the application of polymer coatings, which limit the release of alloying element ions. In addition, biodegradable polymer coatings can serve as a carrier for drugs and other substances. The paper presents the results of research on the physical properties of biodegradable polymer coatings containing nanoparticle hydroxyapatite on a titanium alloy substrate. Methods: A PLGA coating was used in the tests. The coatings on the substrate of the anodized Ti6Al7Nb alloy were applied by ultrasonic spray coating. The tests were carried out for coatings with various hydroxyapatite content (5, 10, 15, 20%) and thickness resulting from the number of layers applied (5, 10, 15 layers). The scope of the research included microscopic observations using scanning electron microscopy, topography tests with optical profilometry, structural studies using X-ray diffraction, as well as wettability and adhesion tests. Results: The results shows that with the use of ultrasonic spray coating system is possible to obtain the continuous coatings containing hydroxyapaptite. Conclusions: The properties of the coating can be controlled by changing the percentage of hydroxyapatite and the number of layers of which the coating is composed.

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Aims: Dual antiplatelet therapy (DAPT) can be shortened up to 1 month in high-bleeding risk (HBR) patients receiving a contemporary biodegradable-polymer sirolimus-eluting stent. We aimed to summarize the evidence on a similar DAPT regimen after biodegradable-polymer everolimus-eluting stent (EES) implantation in patients at HBR. Methods and results: We pooled the individual participant data from the available trials evaluating this strategy, namely, the SENIOR and the POEM trials. Inclusion criteria were ≥1 biodegradable-polymer EES implantation and ≤1-month duration of DAPT. The primary endpoint was the 1-year composite of cardiovascular death, myocardial infarction, or stroke. Major bleeding was defined as Bleeding Academic Research Consortium (BARC) type 3-5 bleeding. Landmark analyses were performed at 1 month, the time point for intended DAPT interruption. We included 766 participants (age 77.5 ± 8.2 years, women 31.9%), 323 from the SENIOR and 443 from the POEM trial. The primary endpoint occurred in 45 participants (6.0%; 95% confidence interval [CI], 4.3-7.7%) through 1 year of follow-up, with 21 (2.8%; 95% CI, 1.6-3.9%) events during the first month and 24 (3.4%; 95% CI, 2.0-4.7%) thereafter. The incidences of cardiovascular death, myocardial infarction, and stroke were 2.2% (95% CI, 0.36-2.50%), 3.1% (95% CI, 1.8-4.3%), and 1.2% (95% CI, 0.4-2.0%), respectively. BARC type 3-5 bleeding ocuurred in 1.1% (95% CI, 0.3-1.8%) at 1 month and 2.9% (95% CI, 1.6-4.1%) at 1 year. Conclusion: HBR patients receiving biodegradable-polymer EES had few ischemic and bleeding events when given 1 month of DAPT. One-month DAPT after biodegradable-polymer EES implantation seems safe in patients at HBR.

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The resorption rate of bioresorbable implants requires tuning to match the desired field of application. The use of Mg as implant material is highly advantageous, as it provides sufficient mechanical strength combined with its biodegradability. Consequently, the implant vanishes after it has served its intended purpose, allowing the complete restoration of natural tissue and organ function. However, a biodegradable Mg implant requires a biodegradable coating to slow the rate of Mg corrosion, as a permanent coating would negate the benefits of using Mg as an implant material. Therefore, degradable polymers are the materials of choice, especially polyester-based coatings, such as PLLA, as they have been proven in clinical practice over the long term. Within this work, the degradation retarding effect of a physical barrier in form of four clinically relevant polyester-based coatings, poly-l-lactide (PLLA), poly-l-lactide-co-glycolide (PLGA), poly(l-lactide-co-PEG) triblock copolymer (PLLA-co-PEG), and polydioxanone (PDO), is investigated in vitro under pH-static conditions using CO2 gas to compensate pH changes due to Mg corrosion. Coating thicknesses of 7.5 to 8.3 µm were comparable to commercially available stent systems. Quantitative analysis of magnesium concentration in buffered test medium by a photometric assay allows real-time monitoring. Shielding effect of different polyesters through polymer coating and formation of a protective passivation layer beneath the polymer coating was observed and characterized using SEM and EDX techniques. Our finding was that even imperfect polymer layers provide a considerable protective effect, and the used in vitro setup matches reported in vivo observations regarding elemental composition of corrosion products.

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We introduce a two-pronged strategy comprising focused ultrasound (FUS)-mediated blood-brain barrier (BBB) opening and long-circulating biodegradable nanoparticles (NPs) for systemic delivery of nucleic acids to the brain. Biodegradable poly(ß-amino ester) polymer-based NPs were engineered to stably package various types of nucleic acid payloads and enable prolonged systemic circulation while retaining excellent serum stability. FUS was applied to a predetermined coordinate within the brain to transiently open the BBB, thereby allowing the systemically administered long-circulating NPs to traverse the BBB and accumulate in the FUS-treated brain region, where plasmid DNA or mRNA payloads produced reporter proteins in astrocytes and neurons. In contrast, poorly circulating and/or serum-unstable NPs, including the lipid NP analogous to a platform used in clinic, were unable to provide efficient nucleic acid delivery to the brain regardless of the BBB-opening FUS. The marriage of FUS-mediated BBB opening and the long-circulating NPs engineered to copackage mRNA encoding CRISPR-associated protein 9 and single-guide RNA resulted in genome editing in astrocytes and neurons precisely in the FUS-treated brain region. The combined delivery strategy provides a versatile means to achieve efficient and site-specific therapeutic nucleic acid delivery to and genome editing in the brain via a systemic route.

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The wearability of the flexible electronic skin (e-skin) allows it to attach to the skin for human motion monitoring, which is essential for studying human motion and especially for assessing how well patients are recovering from rehabilitation therapy. However, the use of non-degradable synthetic materials in e-skin may raise skin safety concerns. Natural biodegradable polymers with advantages such as biodegradability, biocompatibility, sustainability, natural abundance, and low cost have the potential to be alternative materials for constructing flexible e-skin and applying them to human motion monitoring. This review summarizes the applications of natural biodegradable polymers in e-skin for human motion monitoring over the past three years, focusing on the discussion of cellulose, chitosan, silk fibroin, gelatin, and sodium alginate. Finally, we summarize the opportunities and challenges of e-skin based on natural biodegradable polymers. It is hoped that this review will provide insights for the future development of flexible e-skin in the field of human motion monitoring.

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BACKGROUND: Azospirillum baldaniorum Sp245 produces poly-ß-hydroxybutyrate, a biodegradable polymer with characteristics similar to synthetic thermoplastics, including polypropylene. In the synthesis pathway, the poly-ß-hydroxybutyrate synthase enzyme uses thioesters of 3-hydroxy butyryl-CoA as a substrate and catalyzes their polymerization with HS-CoA release. METHODS: A study was conducted using in silico analysis of the two phbC genes of A. baldaniorum Sp245. One was selected for amplification and cloning into the pEXP5- CT/TOPO® vector, which was analysed by restriction pattern, polymerase chain reaction, and sequencing. SDS-PAGE analysis determined the molecular weight of the PhbC1 protein from Azospirillum baldaniorum (AbPhbC1). The presence of the protein was confirmed by Western blotting using anti-polyhistidine monoclonal antibodies. The enzymatic activity in the crude extract of AbPhbC1 was determined by measuring the concentration of sulfhydryl groups using the Ellman method. A UV-Vis assay was performed. To confirm the presence of the poly-ß-hydroxybutyrate product, an NMR assay was performed. RESULTS: In silico analyses, it is revealed that AbPhbC1 and the PhbC2 protein from Azospirillum baldaniorum (AbPhbC2) retain the poly-ß-hydroxybutyrate polymerase and α/ß hydrolase domain. The Cys-His-Asp catalytic triad is highly conserved in all four polyß-hydroxyalkanoate synthases in the central subdomain, structurally similar to the reported crystallized proteins. The dimerization subdomain is different; in AbPhbC1, it is in the closed form; in AbPhbC2, it is in the open form; and in AbPhbC2, it lacks the EC region as class III and IV poly-ß-hydroxyalcanoate synthases. In vitro, the molecular weight of AbPhbC1 was 68 kDa. The polymerization of PHB by AbPhbC1 was detected by the release of HS-CoA from the quantification of SH. The UV-Vis scan showed a characteristic peak at 264 nm. A comparison of the NMR spectra of the bacterial and commercial poly-ß-hydroxybutyrate samples suggested their presence. CONCLUSION: In silico analyses suggested that AbPhbC1 and AbPhbC2 are structurally functional, except that AbPhbC2 might require the PhaR subunit for its activity; this strongly suggests that it could be a class IV poly-ß-hydroxyalcanoate synthase. UV-Vis scanning and NMR spectroscopy revealed the synthesis of poly-ß-hydroxybutyrate by the A. baldaniorum enzyme AbPhbC1, indicating that the enzyme is functional.

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Amid the current environmental crisis caused by plastic accumulation, one of the proposed solutions to manage this problem is using biodegradable polymers. However, the impact of adding biodegradable polymers to the well-established circular economy of recyclable polymers, such as HDPE, has not been fully considered. Therefore, there is a need to reconsider the way we consume, dispose of, and manage biodegradable polymers after use. This study evaluates the effect of varying the contents of a biodegradable polymer, taking poly(lactic acid) (PLA) as a model biodegradable polymer, on the thermal and mechanical properties of HDPE. The study highlights the importance of identifying and disposing of biodegradable polymers to avoid mixtures with HDPE, in order not to affect mechanical performance when considering reprocessing and a new life cycle of this conventional polymer.

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This research paper reports an enhancement of thermal, optical, mechanical and antibacterial activities of the Polyvinyl alcohol-Nanodiamonds (PVA-NDs) composite required for the food packaging industry. The synthesis of composites was done by the wet processing method. The large surface area of NDs facilitated the robust interaction between the hydroxyl group and macromolecular chains of PVA to enhance the hydrogen bonding of PVA with NDs rather than PVA molecules. Thus, a reduction in PVA diffraction peak intensity was reported. NDs improved the thermal stability by preventing the out-diffusion of volatile decomposition products of PVA. The results also revealed an enhancement in tensile strength (∼60 MPa) and ductility (∼180 %). PVA-NDs composite efficiently blocked the UVC (100 %), most of the part of the UVB (∼85 % above 300 nm), and UVA (∼58 %). Furthermore, enhanced antibacterial activities were reported for PVA-NDs composite against E. coli and S. aureus. NDs accumulated around the bacterial cells prevented essential cellular functions and led to death. Hence, this composite could be a promising candidate for safe, thermally stable, strong, flexible, transparent, UV- resistant antibacterial food packaging material.

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The shelf life of perishable foods is estimated through expensive and imprecise analyses that do not account for improper storage. Smart packaging, obtained by agile manufacturing of nanofibers functionalized with natural pigments from agri-food residues, presents promising potential for real-time food quality monitoring. This study employed the solution blow spinning (SBS) technique for the rapid production of smart nanofiber mats based on polycaprolactone (PCL), incorporating extracts of agricultural residues rich in anthocyanins from eggplant (EE) or purple cabbage (CE) for monitoring food quality. The addition of EE or CE to the PCL matrix increased the viscosity of the solution and the diameter of the nanofibers from 156 nm to 261-370 nm. The addition of extracts also improved the mechanical and water-related properties of the nanofibers, although it reduced the thermal stability. Attenuated total reflectance Fourier-transform infrared spectroscopy confirmed the incorporation of anthocyanins into PCL nanofibers. Nanofiber mats incorporated with EE or CE exhibited visible color changes (ΔE ≥ 3) in response to buffer solutions (pH between 3 and 10), and ammonia vapor. Smart nanofibers have demonstrated the ability to monitor fish fillet spoilage through visible color changes (ΔE ≥ 3) during storage. Consequently, smart nanofibers produced by the SBS technique, using PCL and anthocyanins from agro-industrial waste, reveal potential as smart packaging materials for food.

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Green-synthesis of biodegradable polymeric curcumin-nanoparticles using affordable biodegradable polymers to enhance curcumin's solubility and anti-oxidative potential. The curcumin-nanoparticle was prepared based on the ionic-interaction method without using any chemical surfactants, and the particle-size, zeta-potential, surface-morphology, entrapmentefficiency, and in-vitro drug release study were used to optimise the formulation. The antioxidant activity was investigated using H2DCFDA staining in the zebrafish (Danio rerio) model. The mean-diameter of blank nanoparticles was 178.2 nm (±4.69), and that of curcuminnanoparticles was about 227.7 nm (±10.4), with a PDI value of 0.312 (±0.023) and 0.360 (±0.02). The encapsulation-efficacy was found to be 34% (±1.8), with significantly reduced oxidative-stress and toxicity (∼5 times) in the zebrafish model compared to standard curcumin. The results suggested that the current way of encapsulating curcumin using affordable, biodegradable, natural polymers could be a better approach to enhancing curcumin's water solubility and bioactivity, which could further be translated into potential therapeutics.

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Monodisperse nanoparticles of biodegradable polyhydroxyalkanoates (PHAs) polymers, copolymers of 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB), are synthesized using a membrane-assisted emulsion encapsulation and evaporation process for biomedical resorbable adhesives. The precise control over the diameter of these PHA particles, ranging from 100 nm to 8 µm, is achieved by adjusting the diameter of emulsion or the PHA concentration. Mechanical properties of the particles can be tailored based on the 3HB to 4HB ratio and molecular weight, primarily influenced by the level of crystallinity. These monodisperse PHA particles in solution serve as adhesives for hydrogel systems, specifically those based on poly(N, N-dimethylacrylamide) (PDMA). Semi-crystalline PHA nanoparticles exhibit stronger adhesion energy than their amorphous counterparts. Due to their self-adhesiveness, adhesion energy increases even when those PHA nanoparticles form multilayers between hydrogels. Furthermore, as they degrade and are resorbed into the body, the PHA nanoparticles demonstrate efficacy in in vivo wound closure, underscoring their considerable impact on biomedical applications.

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The in vivo fate of chemotherapeutic drugs plays a vital role in understanding the therapeutic outcome, side effects, and the mechanism. However, the lack of imaging abilities of drugs, tedious labeling processes, and premature leakage of imaging agents result in loss of fidelity between the drugs and imaging signals. Herein, an amphiphilic polymer is created by copolymerization of a near-infrared-II (NIR-II) fluorophore tracer (T) and an anticancer Pt(IV) prodrug (D) of cisplatin in a hand-holding manner into one polymer chain for the first time. The obtained PolyplatinDT is capable of delivering the drugs and the fluorophores concomitantly at a precise D/T ratio, thereby resulting in tracking the platinum drugs and even readout of them in real-time via NIR-II imaging. PolyplatinDT can self-assemble into nanoparticles, referred to as NanoplatinDT. Furthermore, a caspase-3 cleavable peptide that serves as an apoptosis reporter is attached to NanoplatinDT, resulting in NanoplatinDTR that are capable of simultaneously tracking platinum drugs and evaluating the therapeutic efficacy. Overall, it is reported here the design of the first theranostic polymer with anticancer drugs, drug tracers, and drug efficacy reporters that can work in concert to provide insight into the drug fate and mechanism of action.

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In this study, we determined effects of an anionic siRNA delivery vector, siRNA ternary complex, which is constructed with biodegradable dendrigraft poly-L-lysine (DGL) and γ-polyglutamic acid (γ-PGA) on the melanoma cells and melanoma lung metastasis. The siRNA ternary complex showed high cellular uptake and silencing effect in melanoma cell line B16-F10/Luc cells. After intravenous administration of the siRNA ternary complex, high silencing effect was also observed in the lung of B16-F10/Luc melanoma metastasis model mice. Therefore, we applied vascular endothelial growth factor (VEGF)-siRNA on the siRNA ternary complex and determined the effect on the melanoma lung metastasis. The siRNA ternary complex containing VEGF-siRNA reduced VEGF protein levels significantly in in vitro and in vivo, and the complex successfully inhibited melanoma lung metastasis. This biodegradable and effective siRNA delivery vector, siRNA ternary complex, could be available for clinical trials.

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Tissue engineering has emerged as an advanced strategy to regenerate various tissues using different raw materials, and thus it is desired to develop more approaches to fabricate tissue engineering scaffolds to fit specific yet very useful raw materials such as biodegradable aliphatic polyester like poly (lactide-co-glycolide) (PLGA). Herein, a technique of 'wet 3D printing' was developed based on a pneumatic extrusion three-dimensional (3D) printer after we introduced a solidification bath into a 3D printing system to fabricate porous scaffolds. The room-temperature deposition modeling of polymeric solutions enabled by our wet 3D printing method is particularly meaningful for aliphatic polyester, which otherwise degrades at high temperature in classic fuse deposition modeling. As demonstration, we fabricated a bilayered porous scaffold consisted of PLGA and its mixture with hydroxyapatite for regeneration of articular cartilage and subchondral bone. Long-termin vitroandin vivodegradation tests of the scaffolds were carried out up to 36 weeks, which support the three-stage degradation process of the polyester porous scaffold and suggest faster degradationin vivothanin vitro. Animal experiments in a rabbit model of articular cartilage injury were conducted. The efficacy of the scaffolds in cartilage regeneration was verified through histological analysis, micro-computed tomography (CT) and biomechanical tests, and the influence of scaffold structures (bilayerversussingle layer) onin vivotissue regeneration was examined. This study has illustrated that the wet 3D printing is an alternative approach to biofabricate tissue engineering porous scaffolds based on biodegradable polymers.

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