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Although polymers tend not to mix, it remains challenging to characterize the immiscibility of enantiomeric poly(ʟ-lactide) (PLLA) and poly(ᴅ-lactide) (PDLA), particularly with equivalent and high molecular weight (high MW), which frustratingly disfavors the exclusive stereocomplexation. By introducing a random copolymer (PLC) of ʟ-lactide and caprolactone to form binary blends with PLLA and PDLA, the phase behavior of high-MW PLLA/PDLA blends was investigated mainly by using differential scanning calorimetry (DSC) and atomic force microscopy (AFM). DSC results showed that PLLA/PLC blends exhibited a single glass transition temperature (T g ), which depended on the blending ratio and precisely corresponded with the theoretical values calculated from the Fox equation. In comparison, PDLA/PLC blends showed composition-dependent heat-capacity increment at two unchanged T g values of pure PLC and PDLA. AFM observation revealed that PLC is completely miscible with PLLA at high MW but is immiscible with PDLA, logically suggesting immiscibility of high-MW PLLA and PDLA. Moreover, AFM results demonstrated that high-MW PLLA/PDLA blends exhibited spherical droplets in asymmetric blends and bicontinuous interpenetrating worm-like patterns in symmetric counterparts, showing distinct and well-defined interfaces, confirming the microphase separation. Additionally, different MWs fundamentally led to significant differences in miscibility, which consequently affected the crystallization behaviors of PLLA/PDLA blends. This work provides evidence for (im)miscibility and its crucial impact on the crystallization of PLLA/PDLA blends and has important implications for understanding the stereocomplexation of polymers., Competing Interests: Declaration of competing interest All authors declare that they have no any competing financial interests or personal relationships that could have appeared to influence this work., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Birch tar was added to polylactide (PLA) and polycaprolactone (PCL) to create films with antimicrobial properties. After incubating the films for seven days in lake water, the diversity of bacterial communities developed on the surfaces of PCL and PLA with embedded birch tar (1 %, 5 %, and 10 %, w/w) was assessed with amplicon sequencing of the 16S rRNA gene on a MiSeq platform (Illumina). Notably, Aquabacterium and Caulobacter were more abundant at the surface of PCL compared to PLA (13.4 % vs 0.2 %, p < 0.001 and 9.5 % vs 0.2 %, p < 0.001, respectively) while Hydrogenophaga was significantly more abundant at the surface of PLA compared to PCL (6.1 % vs 1.8 %, p < 0.01). Overall, lower birch tar concentrations (1 % and 5 % on both polymers) stimulated bacterial diversity in biofilms compared to the control. The number of reeds assigned to Flavobacterium and Aquabacterium showed a rising trend with the increase of birch tar concentration on the surface of both polymers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Stereocomplex (SC) crystallization can prominently improve the physico-chemical properties of poly(l-lactide)/poly(d-lactide) (PLLA/PDLA) blends, yielding a novel polylactide (PLA) material. However, the predominant formation of SC crystals in the melt-processing of high-molar-mass (high-MW, >100 kg/mol) enantiomeric PLA blends remains a huge challenge due to the competition between SC crystallization and homocrystallization. Herein, double-grafted copolymer having both PLLA and PDLA side chain has been designed and synthesized as an efficient crystallization promoter for the harvest of SC crystals in the high-MW PLLA/PDLA blends. The results show that, with the addition of such a copolymer, the blends can preferentially crystallize into SC crystals in both isothermal and non-isothermal conditions. Promisingly, the SC crystals can be exclusively formed by adding only small amounts (e.g., 0.5 wt%) of the copolymer, without the formation of any homocrystals. This interesting observation can be interpreted by the crucial role of the unique copolymer in suppressing the phase separation of the opposite PLA enantiomers upon melting as an efficient compatibilizer and then encouraging the generation of alternatingly arranged PLLA/PDLA chain clusters favored for SC nucleation and crystal growth. These findings provide new inspiration for the development of high-performance PLA with desirable SC crystallizability., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

3D printing is a promising technique for obtaining bone implants. However, 3D printed bone implants, especially those printed using fused deposition modelling, are still in the experimental phase despite decades of work. Research on new materials faces numerous limitations, such as reagents' cost and machines' high prices to produce filaments for 3D printing polymer-ceramic composites for fused deposition modelling. This paper presents a simple, low-cost, and fast method of obtaining polymer-ceramic filaments using apparatus consisting of parts available in a hardware store. The method's versatility for producing the filaments was demonstrated on two different biodegradable polymers - polylactic acid and polycaprolactone - and different concentrations of calcium phosphate - β-tricalcium phosphate - in the composite, up to 50 % by weight. For screening purposes, numerous scaffolds were 3D printed from the obtained filaments on a commercial 3D printer. Structural, mechanical, and biological tests show that the 3D printed scaffolds are suitable for bone implants, as their structure, mechanical, and non-cytotoxic properties are evident. Moreover, the proposed method of composite forming is a simplification of the processes of manufacturing and researching 3D printed materials with potential applications in the regeneration of bone tissue., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Polymer melt strength (MS) is strongly correlated with its molecular structure, while their relationship is not very clear yet. In this work, designable long-chain branched polylactide (LCB-PLA) is prepared in situ by using a tailor-made (methyl methacrylate)-co-(glycidyl methacrylate) copolymer (MG) with accurate number of reactive sites. A new concept of branching density (φ) in the LCB-PLA system is defined to quantitively study their relationship. Importantly, a critical point of φ c  = 5.5 mol/10 4  mol C is revealed for the first time, below which the zero-shear viscosity (η 0 ) corresponding to MS increases slowly with a slope of Δη 0 /Δφ = 1400, while it increases sharply above this critical point due to entanglement of neighboring LCB-PLA chains. Consequently, the MS of PLA increased by >100 times by optimizing the LCB structures while maintaining processibility. Therefore, this work provides a deeper understanding and feasible route in quantitative design of polymers with high(er) melt strength for some specialty applications., (© 2023 Wiley-VCH GmbH.)

Porous polymer microspheres are employed in biotherapeutics, tissue engineering, and regenerative medicine. Porosity dictates cargo carriage and release that are aligned with the polymer physicochemical properties. These include material tuning, biodegradation, and cargo encapsulation. How uniformity of pore size affects therapeutic delivery remains an area of active investigation. Herein, we characterize six branched aliphatic hydrocarbon-based porogen(s) produced to create pores in single and multilayered microspheres. The porogens are composed of biocompatible polycaprolactone, poly(lactic-co-glycolic acid), and polylactic acid polymers within porous multilayered microspheres. These serve as controlled effective drug and vaccine delivery platforms., Competing Interests: Declaration of competing interest F.S., M.P., B.D.K and H.E.G. are named inventors on provisional patents for the new porogens and LBL MS design for SARS-CoV-2 antigen loading as described in this report (63/286,304, 63/158,484). F.S., M.P., B.D.K and H.E.G. hold a patent on ‘Microparticle compositions and methods use thereof’ (Docket No. 21069PCT, Serial No. PCT/US2022/01950). H.E.G is the co-founder of Exavir Therapeutics., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Bioplastics are one of the answers to environmental pollution and linear material flows. The most promising bioplastic polylactide (PLA) is already replacing conventional plastics in a number of applications. The properties of PLA, however, do not fit for all potential application areas, but they can be altered by the introduction of comonomers. The copolymerization of lactide (LA) with other lactones like ϵ-caprolactone (CL) has been established for several years. Nevertheless, controlling copolymerizations remains a challenge due to the high complexity of the system. Copolymerization of LA with other monomer classes is much less investigated, but has the chance to overcome the limitations in material properties that occur when only lactones are used. The crucial factor for all copolymerizations is the catalyst. It dominates the reaction kinetics and determines the resulting microstructure. In this review, copolymerization catalysts for LA are presented divided into catalysts for the synthesis of lactone block copolymers, lactone random copolymers, and multimechanistically synthesized copolymers. The selected catalysts are highlighted either owing to their industrially applicable polymerization conditions or their non-standard mechanism., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

In the present contribution, a new strategy for preparing block copolymers of polylactide (PLA), a bio-derived polymer of increasing importance, is described. The method should lead to multiblock copolymers of lactide with vinyl monomers (VM), i.e., monomers that polymerize according to different mechanisms, and is based on the introduction of multiple "inifer" ( INItiator/transFER agent ) groups into PLA's structure. As an "inifer" group, tetraphenylethane (TPE, known to easily thermally dissociate to radicals) was incorporated into PLA chains using diisocyanate. PLA that contained TPE groups (PLA-PU) was characterized, and its ability to form initiating radicals was demonstrated by ESR measurements. PLA-PU was used as a "macroinifer" for the polymerization of acrylonitrile and styrene upon moderate heating (85 °C) of the PLA-PU in the presence of monomers. The formation of block copolymers PLA/PVM was confirmed by 1 H NMR, DOSY NMR, and FTIR spectroscopies and the SEC method. The prepared copolymers showed only one glass transition in DSC curves with T g values higher than those of PLA-PU., Competing Interests: The authors declare no conflicts of interest.

The recent growth of polymer 3D-printing has brought innovation to the medical implant field. Implants with complex porous structures can be fabricated by printing to tune mechanical behavior and enable diffusion, consequently improving integration with tissues in the human body. Poly(L-lactide-co-ε-caprolactone) (PLCL) is a 3D-printable polymer that possess a wide range of possible mechanical properties depending on its monomer composition. It is often used in biomedical applications requiring degradability. In this study, we explore 1) the effect of annealing 3D-printed PLCL and 2) the degradation profile of both annealed and unannealed 3D-printed PLCL scaffolds. The degraded samples were characterized for its molecular weight, mass loss, microstructure, and mechanical properties. By annealing the 3D-printed PLCL, we reveal the structure-property relationship of PLCL. Crystallization was found to be a crucial factor in the resulting mechanical properties, increasing stiffness significantly. The subsequent degradation study revealed that there was no significant difference brought about by pre-annealing the scaffolds. The scaffolds were found to maintain their mechanical properties until up to 8 weeks, at which point the scaffolds reached a critical molecular weight and lost their mechanical integrity., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Shape-memory and self-healing polymers have been a hotspot of research in the field of smart polymers in the past decade. Under external stimulation, shape-memory and self-healing polymers can complete programed shape transformation, and they can spontaneously repair damage, thereby extending the life of the materials. In this review, we focus on the progress in polymers with shape-memory and self-healing properties in the past decade. The physical or chemical changes in the materials during the occurrence of shape memory as well as self-healing were analyzed based on the polymer molecular structure. We classified the polymers and discussed the preparation methods for shape-memory and self-healing polymers based on the dynamic interactions which can make the polymers exhibit self-healing properties including dynamic covalent bonds (DA reaction, disulfide exchange reaction, imine exchange reaction, alkoxyamine exchange reaction, and boronic acid ester exchange reaction) and dynamic noncovalent interactions (crystallization, hydrogen bonding, ionic interaction, metal coordination interaction, host-guest interactions, and hydrophobic interactions) and their corresponding triggering conditions. In addition, we discussed the advantages and the mechanism that the shape-memory property promotes self-healing in polymers, as well as the future trends in shape-memory and self-healing polymers.

Micelles from self-assembled amphiphilic copolymers are highly attractive in drug delivery, due to their small size and hydrophilic stealth corona allowing prolonged lifetimes in the bloodstream and thus improved drug bioavailability. Polylactide (PLA)-based amphiphilic copolymer micelles are key candidates in this field, owing to the well-established biodegradability and biocompatibility of PLA. While PLA-b-poly(ethylene glycol) (PEG) block copolymer micelles can be seen as the "gold standard" in drug delivery research so far, the progresses in controlled radical polymerizations (Atom Transfer Radical Polymerization, Reversible Addition-Fragmentation Transfer and Nitroxide Mediated Polymerization) have offered new opportunities in the design of advanced amphiphilic copolymers for drug delivery due to their flexibility in many regards: (i) they can be easily combined with ring-opening polymerization (ROP) of lactide, with a diversity in types of architectures (e.g., block, graft, star), (ii) they allow (co)polymerization of a wide range of vinyl monomers, possibly circumventing PEG limitations, (iii) functionalization (with biomolecules or stimuli-cleavable moieties) is versatile due to end-group fidelity and copolymerization ability with reactive/functional comonomers. In this review, we report on the advances in the past decade of such amphiphilic PLA/vinyl polymer based nano-carriers, regarding key properties such as stealth character, cell targeting and stimuli-responsiveness., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this study, in situ reactive extrusion of polylactide and thermoplastic starch modified with chloropropyl trimethoxysilane coupling agent (PLA/mTPS) is proposed. The success of covalent bond formation between PLA matrix and mTPS phase is clarified by two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy with 1 H 1 H TOCSY mode. This chemically bound PLA with starch gives the remarkable compatibility in the PLA/mTPS film, with not only a decreased glass transition temperature (47 °C) but also an increased crystallinity of PLA (Χ c of 50%). It consequently increases oxygen barrier significantly and also enhances the film flexibility as observed from the drastic increase of elongation at break (from 3% to 50%). Moreover, the PLA/mTPS 60/40 (w/w) film exhibits the accelerated degradation as compared with pure PLA film., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The paper presents a synthesis of poly(l-lactide) with bacteriostatic properties. This polymer was obtained by ring-opening polymerization of the lactide initiated by selected low-toxic zinc complexes, Zn[(acac)(L)H 2 O], where L represents N-(pyridin-4-ylmethylene) tryptophan or N-(2-pyridin-4-ylethylidene) phenylalanine. These complexes were obtained by reaction of Zn[(acac) 2 H 2 O] and Schiff bases, the products of the condensation of amino acids and 4-pyridinecarboxaldehyde. The composition, structure, and geometry of the synthesized complexes were determined by NMR and FTIR spectroscopy, elemental analysis, and molecular modeling. Both complexes showed the geometry of a distorted trigonal bipyramid. The antibacterial and antifungal activities of both complexes were found to be much stronger than those of the primary Schiff bases. The present study showed a higher efficiency of polymerization when initiated by the obtained zinc complexes than when initiated by the zinc(II) acetylacetonate complex. The synthesized polylactide showed antibacterial properties, especially the product obtained by polymerization initiated by a zinc(II) complex with a ligand based on l-phenylalanine. The polylactide showed a particularly strong antimicrobial effect against Pseudomonas aeruginosa, Staphylococcus aureus, and Aspergillus brasiliensis . At the same time, this polymer does not exhibit fibroblast cytotoxicity.

Innovations in food and drink packaging result mainly from the needs and requirements of consumers, which are influenced by changing global trends. Antimicrobial and active packaging are at the forefront of current research and development for food packaging. One of the few natural polymers on the market with antimicrobial properties is biodegradable and biocompatible chitosan. It is formed as a result of chitin deacetylation. Due to these properties, the production of chitosan alone or a composite film based on chitosan is of great interest to scientists and industrialists from various fields. Chitosan films have the potential to be used as a packaging material to maintain the quality and microbiological safety of food. In addition, chitosan is widely used in antimicrobial films against a wide range of pathogenic and food spoilage microbes. Polylactic acid (PLA) is considered one of the most promising and environmentally friendly polymers due to its physical and chemical properties, including renewable, biodegradability, biocompatibility, and is considered safe (GRAS). There is great interest among scientists in the study of PLA as an alternative food packaging film with improved properties to increase its usability for food packaging applications. The aim of this review article is to draw attention to the existing possibilities of using various components in combination with chitosan, PLA, or bacteriocins to improve the properties of packaging in new food packaging technologies. Consequently, they can be a promising solution to improve the quality, delay the spoilage of packaged food, as well as increase the safety and shelf life of food.

Although biodegradable polymers were widely researched, this is the first study considering the effect of combined testing environments and cyclic loading on the most important aspect related to additive manufacturing: the interfacial bond between deposited layers. Its results give confidence in applicability of the material extrusion additive manufacturing technology for biomedical fields, by demonstrating that the interface behaves in a manner similar to that of the bulk-polymer material. To do this, especially designed tensile specimens were used to analyse the degradation of 3D-printed polymers subjected to constant-amplitude and incremental cyclic loads when tested in air at room temperature (control) and submerged at 37 °C (close to in-vivo conditions). The mechanical properties of the interface between extruded filaments were compared against the bulk material, i.e. along filaments. In both cases, cyclic loading caused only a negligible detrimental effect compared to non-cyclic loading (less than 10 % difference in ultimate tensile strength), demonstrating the suitability of using 3D-printed components in biomedical applications, usually exposed to cyclic loading. For cyclic tests with a constant loading amplitude, larger residual deformation (>100 % greater) and energy dissipation (>15 % greater) were found when testing submerged in solution at 37 °C as opposed to in laboratory conditions (air at room temperature), as used by many studies. This difference may be due to plasticisation effects of water and temperature. For cyclic tests with incrementally increasing loading amplitudes, the vast majority of energy dissipation happened in the last two cycles prior to failure, when the polymer approached the yield point. The results demonstrate the importance of using an appropriate methodology for biomedical applications; otherwise, mechanical properties may be overestimated., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Porous polymer materials derived from poly(ethylene glycol dimethacrylate) (poly-EGDMA) and antibiotic containing polylactide (PLA) are obtained for the first time. Porous poly-EGDMA monoliths with a system of open interconnected pores are synthesized by a visible light-induced radical polymerization of EGDMA in the presence of 70 wt% of porogenic agent, e.g., 1-butanol, 1-hexanol, 1-octanol, or cyclohexanol. The porosity of the obtained polymers is 75-78%. A modal pore size depends on the nature of the porogen and varies from 0.5 µm (cyclohexanol) to 12 µm (1-butanol). The polymer matrix made with 1-butanol features the presence of pores ranging from 1 to 100 µm. The pore surface of poly-EGDMA matrices is inlayered with poly-D,L-lactide (M n  23 × 10 3  Da, PDI 1.31). The PLA-modified poly-EGDMA retains a porous structure that is similar to the initial poly-EGDMA but with improved strength characteristics. The presence of antibiotic containing PLA ensures a high and continuous antibacterial activity of the hybrid polymeric material for 7 days. The nontoxicity of all the porous matrices studied makes them promising for clinical tests as osteoplastic materials., (© 2021 Wiley-VCH GmbH.)

Over the past 25 years, cannabis plants have gained major popularity in the research community. This study aimed to evaluate the antioxidant capacity and stabilization efficiency of cannabidiol (CBD) extract in two different polymers: polylactide (PLA) and ethylene-norbornene copolymer (Topas) that are used in packaging materials more often. The research technology included weathering in a special chamber, surface free energy and color change measurements, surface morphology and Fourier-transform infrared spectroscopy (FTIR) analysis, thermogravimetry, and determination of the oxidation induction time or temperature (OIT) values, based on which the effectiveness of the cannabidiol extract could be estimated. Obtained results showed that the addition of CBD to polymer mixtures significantly increased their resistance to oxidation, and it can be used as a natural stabilizer for polymeric products. Moreover, samples with cannabidiol changed their coloration as a result of weathering. Therefore, this natural additive can also be considered as a colorimetric indicator of aging that informs about the changes in polymeric materials during their lifetime. On the other hand, surface properties of samples with cannabidiol content did not alter much compared to pure Topas and PLA.

Cellulose was modified by formic acid to prepare formyl cellulose (FC). The amount of formyl groups in FC was adjusted by controlling the reaction time, reaction temperature, and formic acid concentration. Then, FC was used to reinforce polylactic acid (PLA) films prepared by solution casting. Scanning electron microscopy (SEM) shows that long rod-like cellulose particles were broken into short rods after formylation and the introduction of FC made PLA surface rougher. The mechanical properties of PLA/FC films were improved by the inclusion of FC. Compared to pure PLA film, the PLA/FC composite film with 1 wt% FC (containing 15.79% formyl groups) showed a 48.59% increase in tensile strength and a 346% increase in Young's modulus. The addition of FC also resulted in better water barrier properties. The moisture absorption capacity and water vapor permeability were 40.56% and 51.43% lower than those of the pure-PLA film. The enhancement in properties for PLA/FC composites could be ascribed to the improved compatibility between PLA and cellulose with the introduction of hydrophobic formate groups. The PLA/FC composite films developed in this work could be highly potential for food packaging., Competing Interests: Declaration of competing interest None., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This research work reports the potential of maleinized linseed oil (MLO) as biobased compatibilizer in polylactide (PLA) and a thermoplastic elastomer, namely, polystyrene -b- (ethylene -ran- butylene) -b- styrene (SEBS) blends (PLA/SEBS), with improved impact strength for the packaging industry. The effects of MLO are compared with a conventional polystyrene -b- poly(ethylene -ran- butylene) -b- polystyrene -graft- maleic anhydride terpolymer (SEBS -g- MA) since it is widely used in these blends. Uncompatibilized and compatibilized PLA/SEBS blends can be manufactured by extrusion and then shaped into standard samples for further characterization by mechanical, thermal, morphological, dynamical-mechanical, wetting and colour standard tests. The obtained results indicate that the uncompatibilized PLA/SEBS blend containing 20 wt.% SEBS gives improved toughness (4.8 kJ/m 2 ) compared to neat PLA (1.3 kJ/m 2 ). Nevertheless, the same blend compatibilized with MLO leads to an increase in impact strength up to 6.1 kJ/m 2 , thus giving evidence of the potential of MLO to compete with other petroleum-derived compatibilizers to obtain tough PLA formulations. MLO also provides increased ductile properties, since neat PLA is a brittle polymer with an elongation at break of 7.4%, while its blend with 20 wt.% SEBS and MLO as compatibilizer offers an elongation at break of 50.2%, much higher than that provided by typical SEBS -g- MA compatibilizer (10.1%). MLO provides a slight decrease (about 3 °C lower) in the glass transition temperature ( T g ) of the PLA-rich phase, thus showing some plasticization effects. Although MLO addition leads to some yellowing due to its intrinsic yellow colour, this can contribute to serving as a UV light barrier with interesting applications in the packaging industry. Therefore, MLO represents a cost-effective and sustainable solution to the use of conventional petroleum-derived compatibilizers.

This work reports the versatility of polydopamine (PD) when applied as a particle coating in a composite of polylactide (PLA). Polydopamine was observed to increase the particle-matrix interface strength and facilitate the adsorption of drugs to the material surface. Here, barium sulfate radiopaque particles were functionalized with polydopamine and integrated into a polylactide matrix, leading to the formulation of a biodegradable and X-ray opaque material with enhanced mechanical properties. Polydopamine functionalized barium sulfate particles also facilitated the adsorption and release of the antibiotic levofloxacin. Analysis of the antibacterial capacity of these composites and the metabolic activity and proliferation of human dermal fibroblasts in vitro demonstrated that these materials are non-cytotoxic and can be 3D printed to formulate complex biocompatible materials for bone fixation devices.

Self-stabilizing biodegradable microcarriers were produced via an oil/water solvent evaporation technique using amphiphilic chitosan-g-polyester copolymers as a core material in oil phase without the addition of any emulsifier in aqueous phase. The total yield of the copolymer-based microparticles reached up to 79 wt. %, which is comparable to a yield achievable using traditional emulsifiers. The kinetics of microparticle self-stabilization, monitored during their process, were correlated to the migration of hydrophilic copolymer's moieties to the oil/water interface. With a favorable surface/volume ratio and the presence of bioadhesive natural fragments anchored to their surface, the performance of these novel microcarriers has been highlighted by evaluating cell morphology and proliferation within a week of cell cultivation in vitro.

Sponges, which are parasitic on plants widely found in lakes and oceans, represent a vast resource that has yet to be effectively utilised. Sponge spicules (SS), which contain high amounts of silica dioxide, form after long-term biomineralisation. In this study, SS attached to plant bodies were subjected to acid and heat treatments, followed by grinding, to obtain 10-40-nm siliceous sponge spicules (SSS). SSS and polylactic acid (PLA) were then combined to create 50-450-nm PLA/SSS composite nanofibers. The morphology and bioactivity of the electrospun PLA/SSS nanofibers were examined; the tensile, thermal, and water-resistant properties of the fibers were also evaluated. Our results showed a dramatic enhancement in the thermal and tensile properties of PLA with increasing SSS content; specifically, a 3 wt% increase in SSS content resulted in a 47 °C increase in the initial decomposition temperature and a 73.3-MPa increase in Young's modulus. The water resistance of PLA/SSS increased with SSS content, as indicated by the increase in the water contact angle compared with PLA nanofibers. PLA/SSS nanofibers also exhibited slightly enhanced human foreskin fibroblast cell proliferation, good cytocompatibility, and an antibacterial effect. The enhanced antibacterial and biodegradable properties of PLA/SSS are expected to be useful in biomedical material applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Bio-degradable/bio-compatible poly(lactide-co-glycidyl methacrylate), P(LA-co-GMA), a copolymer has been synthesized. The material contains curable CC groups, which enable its self-curing and grafting reactions with other vinyl monomers. The copolymer was grafted with a pH-responsive polyacrylamide (PAAm), by UV-assisted reactions using acrylamide (AAm) and N,N'-methylene bisacrylamide monomers, and various photoinitiator systems. The original copolymer and its partially-cured counterpart were employed in the grafting reaction. Chemical structures and properties of the resulting materials were characterized. Standard quantitative analysis techniques for measurement of the grafted AAm content and the degree of CC conversion have been developed by 1 H NMR and FTIR spectroscopy. FTIR offers more advantages, in terms of non-destructive analysis, ease of operation, and lower cost of analysis. The results show that the grafted products from pre-cured P(LA-co-GMA) copolymers contain higher grafted AAm contents than their uncured counterparts. The highest grafted AAm content was obtained by using benzophenone (BP) as an initiator, while camphorquinone (CQ) led to the lowest content. In contrast, the degree of CC conversion of the copolymer from the two initiator systems shows a reverse trend. These amphiphilic and pH-responsive grafted copolymers with tunable AAm contents have a high potential for use in various applications, especially in biomedical and environmental fields., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Poly[2-( tert-butylaminoethyl) methacrylate] (PTA), an important class of antimicrobial polymers, has demonstrated its great biocidal efficiency, favorable nontoxicity, and versatile applicability. To further enhance its antimicrobial efficiency, an optimization of the chemical structure of PTA polymers is performed via atom transfer radical polymerization (ATRP) in terms of the antimicrobial ability against Escherichia coli ( E. coli) and Staphylococcus aureus ( S. aureus). After the optimization, the resulting PTA is blended into a polylactide (PLA) matrix to form PTA/PLA composite thin films. It is first found, that the antimicrobial efficiency of PTA/PLA composites was significantly enhanced by controlling the PLA crystallinity and the PLA spherulite size. A possible mechanistic route regarding this new finding has been rationally discussed. Lastly, the cytotoxicity and mechanical properties of a PTA/PLA composite thin film exhibiting the best biocidal effect are evaluated for assessing its potential as a new material for creating antimicrobial biomedical devices.

Polylactide (PLA)-based amphiphilic block copolymers and their nanoassemblies designed with stimuli-responsive degradation (SRD) hold great potential as promising candidates for tumor-targeting drug delivery. However, most of the smart PLA-based nanoassemblies are designed to respond to a single stimulus (typically reduction or acidic pH). Herein, a new strategy is reported to synthesize PLA-based block copolymer micelles exhibiting dual SRD at dual locations (DL-DSRD). The strategy utilizes a combination of ring opening polymerization, controlled radical polymerization, and facile coupling reactions to synthesize an ABA-type PLA-based triblock copolymer with a hydrophilic polymethacrylate (A) and PLA (B) blocks. Incorporation of an acidic pH-responsive ketal linkage in the center of PLA block and reduction-responsive disulfide linkages at PLA/hydrophilic polymethacrylate blocks ensure the formation of smart nanoassemblies featured with ketal linkages in the PLA cores and disulfide linkages at core/corona interfaces, thus attaining DL-DSRD. Such dual acidic pH/reduction-responses at dual locations lead to not only shedding of coronas at interfaces but also destabilization of cores, resulting in the synergistic and accelerated release of encapsulated model drugs, compared with the single stimulus systems. These results, along with lower cytotoxicity, suggest that DL-DSRD strategy can offer versatility in the development of tumor-targeting drug delivery nanocarriers., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The interaction of polymer nanocapsules (NC) prepared from four biodegradable polyesters with variable polymer hydrophobicity (PCL, PLA, PLGA and PLA-PEG) was investigated in the non-phagocytic Vero, Caco-2 and HepG2 cell lines. The NC, labeled with the highly lipophilic fluorescent indocarbocyanine dye DIL, had very similar sizes (approx. 140 nm) and negative zeta-potentials. Asymmetric flow field-flow fractionation evidenced NC colloidal stability and negligible transfer of the dye to serum proteins in the incubation medium. The cytotoxicity of the NC was evaluated via MTT assay over a large polymer concentration range (1-1000 μg/mL) and time of exposure (2, 24 and 48 h). The NC were safe in vitro up to a concentration of approx. 100 μg/mL or higher, depending on the cell line and nature of the polymer. Vero cells were more sensitive to the NC, in particular NC of the more hydrophobic polymer. The cells were exposed to endocytosis inhibitors, incubated with NC, and the cell-associated fluorescence was quantified by spectrofluorometry. HepG2 cells presented a 1.5-2-fold higher endocytic capacity than Caco-2 and Vero cells. The main mechanism of NC uptake was caveolin-mediated endocytosis in HepG2 and Vero cells, and macropinocytosis in Caco-2 cells. Polymer hydrophobicity had an effect on the level of NC associated to HepG2 cells and to a lesser extent on the endocytosis mechanisms in Vero and Caco-2 cells. The NC uptake levels and endocytosis mechanisms differed significantly between cell lines tested., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The aim of the present work was the synthesis and study the kinetics and profiles of camptothecin (CPT) release form block co- and ter-polymer conjugates comprising polylactide (PLA) segments and CPT moieties, structurally diverse by degrees of branching, content of d-PLA units and poly(ethylene glycol) methyl ether methacrylate (PEGMA). Six PLA, non-toxic macroinitiators (MIs), terminated with α-bromoester were synthesized. MIs were subjected to polymerization of CPT methacrylic derivative (CPTMA) with PEGMA at various ratios. The average contents of CPT from elemental analysis, NMR and UV-GPC were approximate to each other. The number of CPT molecules and PEGMA units was in the range of 9-195 and 0-280 per conjugate, respectively. PEGMA units plasticized PLA causing increase of its crystallinity, whereas 7% and more of d-PLA caused material amorphous. PEGMA units decreased thermal stability of conjugates, however it compatibillized the separated phases of PLA and PCPTMA, based on AFM. In vitro release rate of CPT from linear PLA conjugates deposited on injection-molded PLA bars increased by introduction of PEGMA units with zero-order kinetics and Korsmeyer-Peppas model indicating the super case II transport. Branched conjugates revealed some burst release and then the release was rather of first-order-kinetics with respect to CPT with non-Fickian transport., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Over the past two decades, biomass-derived and biodegradable polylactide (PLA) has sparked tremendous attention as a sustainable alternative to traditional petroleum-derived polymers for diverse applications. Unfortunately, the current applications of PLA have been mainly limited to biomedical and commodity fields, mostly because the poor heat resistance (resulting from low melting temperature) and hydrolysis stability make it hard to use as an engineering plastic. Stereocomplexation between enantiomeric poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) opens a new avenue toward PLA-based engineering plastics with improved properties. The formation, crystal structure, properties, and potential applications of stereocomplex-type PLA (SC-PLA) are summarized by some research groups. However, since it is challenging to achieve full stereocomplexation from high-molecular-weight PLLA/PDLA blends and to avoid serious thermal degradation of the PLAs after complete melting, the advances and progress in the processing of SC-PLA into useful products are quite rare in open publication. In this review, some important strategies for enhancing stereocomplex crystallization in practical processing operations are presented and recently developed processing technologies for SC-PLA are highlighted, such as low-temperature sintering. Furthermore, major challenges and future developments are briefly discussed. This review is expected to potentially open up new research activities in the processing of SC-PLA., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polylactide (PLA) is biocompatible and FDA-approved for clinical use and thus has been a choice of the materials valuable for extensive applications in biomedical fields. However, conventionally designed PLA-based amphiphilic block copolymer (ABP) nanoassemblies exhibit slow and uncontrolled release of encapsulated drugs because of the slow biodegradation of hydrophobic PLA in physiological conditions. To improve potentials for clinical use and commercialization of conventional PLA-based nanoassemblies, stimulus-responsive degradation (SRD) platform has been introduced into the design of PLA-based nanoassemblies for enhanced/controlled release of encapsulated drugs. This review summarizes recent strategies that allow for the development of PLA-based ABPs and their self-assembled nanostructures exhibiting SRD-induced enhanced drug release. The review focuses on the design, synthesis, and evaluation of the nanoassemblies as intracellular drug delivery nanocarriers for cancer therapy. Further, the outlook is briefly discussed on the important aspects for the current and future development of more effective SRD PLA-based nanoassemblies toward tumor-targeting intracellular drug delivery.

The shape memory effect (SME) has long been the focus of interest of many research groups that have studied many facets of it, yet to the authors' knowledge some molecular parameters, such as the molecular weight, have been skipped. Thus, the aim of this work is to offer further insight into the shape memory effect, by disclosing the importance of the molecular weight as the relevant parameter dictating the extension of the rubbery plateau, which is the scenario where the entropic network of entanglements manifests. For this, a set of biodegradable amorphous poly(rac-d,l)lactides have been synthesised by ring opening copolymerization of a racemic mixture of L-and D-lactide. The analysis performed on the synthesised enantiomeric copolylactides includes the determination of molecular weights by means of Gel Permeation Chromatography (GPC), thermal properties by Differential Scanning Calorimetry (DSC), dynamic mechanical analysis (DMA) and rheological tests using small amplitude oscillatory flow analysis. Shape memory properties have been determined by means of specific cyclic thermo-mechanic test protocol. It has been shown that the recovery capacity of amorphous PDLLA is linked to the disentanglement time through an exponential law., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Using different type of initiators, the antibacterial moieties are introduced at the chain end of poly(L,L-lactide) (PLLA) and poly(D,D-lactide) (PDLA), and the thermal properties are simultaneously improved using the stereocomplex approach. The physical interaction of polymers and antibacterial compounds is investigated. The double bonds at the chain end are utilized for the interaction of silver ion; however, the silver ions are not detected after stereocomplexation of PLLA and PDLA. On the other hand, catechin (CT) is selected as an initiator precursor of lactide polymerization, protecting the phenolic hydroxyl groups. The linear PLLA and PDLA are obtained by the initiator, resulting in CT conjugated PLAs at the chain end groups after deprotection of phenolic hydroxyl groups. The antibacterial properties are determined by proliferation tests of staphylococcus aureus. The results suggest that the antibacterial properties of CT modified PLAs are derived from the original CT parts., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polylactide (PLA) represents one of the most promising biomedical polymers due to its biodegradability, bioresorbability and good biocompatibility. This work highlights the synthesis and characterization of PLAs using novel diethylzinc/gallic acid (ZnEt₂/GAc) and diethylzinc/propyl gallate (ZnEt₂/PGAc) catalytic systems that are safe for human body. The results of the ring-opening polymerization (ROP) of rac-lactide (rac-LA) in the presence of zinc-based catalytic systems have shown that, depending on the reaction conditions, "predominantly isotactic", disyndiotactic or atactic PLA can be obtained. Therefore, the controlled and stereoselective ROP of rac-LA is discussed in detail in this paper.

PLAcoCL samples, both unaged, termed PLAcoCLu, and aged over time, PLAcoCLa, were prepared and analyzed to study the phase structure, morphology, and their evolution under non-quiescent conditions. X- ray diffraction, Differential Scanning Calorimetry and Atomic Force Microscopy were complemented with thermo-rheological measurements to reveal that PLAcoCL evolves over time from a single amorphous metastable state to a 3 phase system, made up of two compositionally different amorphous phases and a crystalline phase. The supramolecular arrangements developed during aging lead to a rheological complex behavior in the PLAcoCLa copolymer: Around Tt=131 °C thermo-rheological complexity and a peculiar chain mobility reduction were observed, but at T>Tt the thermo-rheological response of a homogeneous system was recorded. In comparison with the latter, the PLLA/PCL 70:30 physical blend counterpart showed double amorphous phase behavior at all temperatures, supporting the hypothesis that phase separation in the PLAcoCLa copolymer is caused by the crystallization of polylactide segment blocks during aging., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Thermo-responsive brush-like amphiphilic poly[2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate]-b-poly(l-lactide)-b-poly[2-(2-methoxyethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methacrylate] [P(MEO2MA-co-OEGMA)-b-PLLA-b-P(MEO2MA-co-OEGMA)] triblock copolymers were synthesized by atom transfer radical polymerization of MEO2MA and OEGMA co-monomers using a α,ω-Bromopropionyl poly(l-lactide) (Br-PLLA-Br) macroinitiator. The resulting copolymers with MEO2MA/OEGMA molar ratio ranging from 79/21 to 42/58 were characterized by (1)H nuclear magnetic resonance and size exclusion chromatography. Thermo-responsive micelles were obtained by self-assembly of copolymers in aqueous medium. The micelles are spherical in shape with sizes varying from 20.7 to 102.5 nm. A hydrophobic anticancer drug, curcumin, was encapsulated in micelles by using membrane hydration method. The properties of drug loaded micelles were determined by dynamic light scattering, transmission electron microscopy and lower critical solution temperature (LCST) measurements. The micelles size decreases from 102.5 nm for blank micelles to 37.6 nm with 10.8% drug loading, suggesting that the drug plays an important role in the micellization procedure. The LCST decreases from 45.1°C for blank micelles to 40.6 and 38.3°C with 5.9 and 10.8% drug loading, respectively. In vitro drug release was performed in pH 7.4 PBS at different temperatures. Data show that the release rate was significantly enhanced above the LCST comparing with that below the LCST. The amount of released drug at 41°C was ca. 20% higher than that at 37°C. Burst-like release was depressed due to enhanced interaction between drug with hydrophobic PLA and PMA chains., (Copyright © 2015. Published by Elsevier B.V.)

PLLA-TMC-GA terpolymer was prepared by ring-opening polymerization of L-lactide, 1, 3-trimethylene carbonate (TMC), and glycolide (GA). The biocompatibility of terpolymer was evaluated in comparison with PLLA and PLLA-TMC with the aim of assessing their potential in the development of bioresorbable cardiovascular stents. Various aspects of in vitro biocompatibility were considered, including MTT assay, hemolytic test, dynamic clotting time, platelet adhesion, platelet activation, protein adsorption, plasma recalcification time and release of cytokines. The results revealed that the terpolymer presents good cytocompatibility and hemocompatibility. Moreover, no significant increase in the release of cytokines was detected. It is thus concluded that these polymers, in particular PLLA-TMC-GA terpolymer present good biocompatibility for cardiovascular applications.

The aim of this work was to investigate the potential of an amphiphilic system comprising chitosan-grafted polylactide and carboxyl-functionalized polylactide acid as a carrier for the controlled release and co-release of two DNA alkylating drugs: doxorubicin and temozolomide. Polylactide and carboxyl-functionalized polylactide acid were obtained through direct melt polycondensation reaction, using methanesulfonic acid as a non-toxic initiator, and subsequently these were grafted to the chitosan backbone through a coupling reaction, utilizing 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide as a condensing agent. ATR-FTIR analysis and conductometric titration confirmed that a reaction between CS and PLA, PLACA2% and PLACA5% occurred. Chitosan-grafted-polylactide and polylactide-citric acid nanoparticles were prepared via the polyelectrolyte complex technique, applying dextran sulphate as a polyanion, and loaded with doxorubicin and temozolomide. The diameter of particles, ζ-potential and their relationship to temperature and pH were analysed in all formulations. Encapsulation, co-encapsulation efficiency and release studies were conducted in different physiological simulated environments and human serum. Results showed the continuous release of drugs without an initial burst in different physiological media., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Stimuli-responsive block copolymers and their self-assembled nanostructures have been extensively studied as effective building blocks in construction of various nanomaterials in nanoscience and nanotechnology. A promising stimuli-responsive platform involves an incorportion of reduction-responsive disulfide linkages that can be cleaved to corresponding thiols when needed. Herein, we describe a novel approach utilizing a combination of ring-opening polymerization and a facile coupling reaction to synthesize a reduction-responsive triblock copolymer comprising biocompatible polylactide (PLA) and poly(ethylene glycol) (PEG) blocks, thus PEG-b(PLA-ss-PLA)-b-PEG (ssBCP). This copolymer self-assembles to form colloidally-stable mono-cleavable micelles having single disulfides in hydrophobic PLA cores surrounded with PEG coronas in aqueous solution. The reductive cleavage of the core disulfides results in changes in micelle morphologies to smaller nanostructures or larger aggregates, depending on the nature of reducing agents. In the presence of glutathione (a cellular reducing agent), the micelle size increases, which enhances the release of encapsulated anticancer drugs in vitro. For biological perspectives, the ssBCP micelles having hydrophilic PEG corona are non-cytotoxic and exhibit enhanced colloidal stability as well as non-specific interactions with proteins., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The strength retention characteristics of oriented semicrystalline polylactides were monitored during hydrolytic degradation in vitro. The effects of the polymer type, the material's initial inherent viscosity (iv), the sample diameter and the residual monomer content on strength retention were analyzed. The analyzed polylactides had similar, but not identical, strength retention characteristics. It was concluded that a higher degree of initial crystallinity was a major variable determining the earlier and more profound strength loss of PLLA than 96L/4D PLA and 80L/20 D,L PLA. Samples with a higher initial iv were found to have a longer strength retention time than lower iv samples. Size-dependency was observed, as the strength retention time was shorter for the smaller diameter samples. This size-dependency was caused by faster iv decay. The amount of residual monomer content had a remarkable impact on strength retention. Neither the sample diameter, initial iv or residual monomer content were found to have an effect on the iv range in which there was a rapid decline in strength properties. Therefore, it was concluded that the inherent viscosity and/or molecular weight of oriented PLLA, 96L/4D PLA and 80L/20 D,L PLA is a major variable determining the strength retention of these materials.

d-glucose end-capped polylactide ruthenium cyclopentadienyl complex (RuPMC) was newly synthesized by a straightforward method. RuPMC was tested against human MCF7 and MDAMB231 breast and A2780 ovarian adenocarcinoma revealing IC50 values in the micromolar range. A pH dependent hydrolysis is advanced by preliminary UV-visible spectroscopy. Cellular distribution studies showed that RuPMC is predominantly found in the nucleus and in the membrane. Data suggest potential application of RuPMC as a new drug delivery system for Ru(II)Cp compounds., (© 2013.)

In this study, the aliphatic N,N‐bisguanidine zinc complex [Zn(DMEG2ch)2](OTf)2 ⋅ THF is introduced as a promising candidate for the chemical recycling of (bio) polyesters. This catalyst is highly active in the ring‐opening polymerization (ROP) of lactide (LA) and ϵ‐caprolactone (CL). The combination of polymerization and depolymerization activity creates new pathways towards a sustainable circular economy. The catalytic activity of [Zn(DMEG2ch)2](OTf)2 ⋅ THF for the chemical recycling of polylactide (PLA) via alcoholysis was investigated by detailed kinetic and thermodynamic studies. It is shown that various high value‐added alkyl lactates can be obtained efficiently under mild reaction conditions. Catalyst recycling was successfully tested using ethanol for the degradation of PLA. In addition, LA can be recovered directly from PLA, enabling either open‐ or closed‐loop recycling. Selective PLA degradation from mixtures with polyethylene terephthalate (PET) and polymer blends are presented. For the first time, a cascade recycling reaction of a PLA/polycaprolactone (PCL) blend is tested with a zinc‐based bisguanidine catalyst, whereby PLA is degraded selectively at first and subsequent modification of the reaction conditions leads to efficient degradation of the remaining PCL. The highly active, universally applicable benign zinc catalyst allows the implementation of a circular plastics economy and thus the reduction of plastic pollution in the environment. [ABSTRACT FROM AUTHOR]

This study focuses on the preparation of hybrid block copolymers of polylactide (PLA) and polystyrene (PS) involving 2,5-dihydroxy-1,4-benzoquinone (DHBQ) as a dual initiator. At the first stage, in the presence of AcONa, 2,5-dihydroxy-1,4-benzoquinone opens the lactide ring, resulting in a carboxylic end group that further facilitates the growth of the PLA chain. The polymerization proceeds at a moderate rate to high conversion degrees to form the polymers with well-defined molecular weight (MW) characteristics. The presence of internal DHBQ fragment in the polymer was proven by IR, UV–VIS, NMR and MALDI-TOF techniques. Obtained polymer can be considered as macroquinone (MQ). The styrene polymerization initiated by MQ/Bu3B proceeds at a moderate rate leading to the formation of hybrid three-arms PLA/PS copolymer. Linear increase in Mn with conversion and polydispersity reduction were observed during copolymerization. As evidenced by relatively low content of polystyrene in the copolymer (8.1 wt. %), the process has a good selectivity. The introduction of styrene units into the copolymer leads to a four-fold increase in E modulus compared to homo-PLA. [ABSTRACT FROM AUTHOR]

ABA types triblock copolymers, specifically poly(L‐lactide)‐co‐poly(ethylene glycol)‐co‐poly(L‐lactide) (PLLA‐PEG‐PLLA) and poly(D‐lactide)‐co‐poly(ethylene glycol)‐co‐poly(D‐lactide) (PDLA‐PEG‐PDLA), are employed for stereocomplexes (SCs) formation. These SCs are subsequently utilized as axles, in conjunction with various cyclodextrins (CDs) as ring moieties to create pseudo‐polyrotaxane (PPRX). The authors referred to this new construct as "SC PPRX", to distinguish it from the earlier study, denoted as "PPRX SC", which primarily focuses on SC within the PPRX. When attempting to form PPRXs in aqueous solutions, the authors encountered challenges related to the inclusion of CDs due to the robust presence of the SC structure. However, by using mixed solvents, such as water/acetone (10/1, v/v), a partial relaxation of the SC structure is observed. This allows for the successful inclusion of CDs, thereby facilitating the PPRX formation. These observations highlight the significance of axle–axle interaction, which, in this case, prevailed over axle–ring interactions in determining the outcome of the formation process. The authors propose the term, 'SC pseudo‐capping effect' to describe this unique phenomenon, underscoring the role of interactions among polymer chains, including polymer–polymer and axle–axle interactions, in shaping the architecture of rotaxanes. This study thus unveils a novel dimension of polymer‐polymer interactions within the realm of rotaxane. [ABSTRACT FROM AUTHOR]

Lactide is one of the most popular and promising monomers for the synthesis of biocompatible and biodegradable polylactide and its copolymers. The goal of this work was to carry out a full cycle of polylactide production from lactic acid. Process conditions and ratios of reagents were optimized, and the key properties of the synthesized polymers were investigated. The influence of synthesis conditions and the molecular weight of lactic acid oligomers on the yield of lactide was studied. Lactide polymerization was first carried out in a 500 mL flask and then scaled up and carried out in a 2000 mL laboratory reactor setup with a combined extruder. Initially, the lactic acid solution was concentrated to remove free water; then, the oligomerization and synthesis of lactide were carried out in one flask in the presence of various concentrations of tin octoate catalyst at temperatures from 150 to 210 °C. The yield of lactide was 67–69%. The resulting raw lactide was purified by recrystallization in solvents. The yield of lactide after recrystallization in butyl acetate (selected as the optimal solvent for laboratory purification) was 41.4%. Further, the polymerization of lactide was carried out in a reactor unit at a tin octoate catalyst concentration of 500 ppm. Conversion was 95%; Mw = 228 kDa; and PDI = 1.94. The resulting products were studied by differential scanning calorimetry, NMR spectroscopy and gel permeation chromatography. The resulting polylactide in the form of pellets was obtained using an extruder and a pelletizer. [ABSTRACT FROM AUTHOR]

Hybrid porous polymers based on poly-EGDMA and polylactide containing vancomycin, the concentration of which in the polymer varied by two orders of magnitude, were synthesized. The processes of polymer biodegradation and vancomycin release were studied in the following model media: phosphate-buffered saline (PBS), trypsin-Versene solution, and trypsin-PBS solution. The maximum antibiotic release was recorded during the first 3 h of extraction. The duration of antibiotic escape from the polymer samples in trypsin-containing media varied from 3 to 22 days, depending on the antibiotic content of the polymer. Keeping samples of the hybrid polymer in trypsin-containing model media resulted in acidification of the solutions—after 45 days, up to a pH of 1.84 in the trypsin-Versene solution and up to pH 1.65 in the trypsin-PBS solution. Here, the time dependences of the vancomycin release from the polymer into the medium and the decrease in pH of the medium correlated. These data are also consistent with the results of a study of the dynamics of sample weight loss during extraction in the examined model media. However, while the polymer porosity increased from ~53 to ~60% the pore size changed insignificantly, over only 10 μm. The polymer samples were characterized by their antibacterial activity against Staphylococcus aureus, and this activity persisted for up to 21 days during biodegradation of the material, regardless of the medium type used in model. Surface-dependent human cells (dermal fibroblasts) adhere well, spread out, and maintain high viability on samples of the functionalized hybrid polymer, thus demonstrating its biocompatibility in vitro. [ABSTRACT FROM AUTHOR]

Electrospinning is a process that has attracted significant interest in recent years. It provides the opportunity to produce nanofibers that mimic the extracellular matrix. As a result, it is possible to use the nonwovens as scaffolds characterized by high cellular adhesion. This work focused on the synthesis of poly(glycerol itaconate) (PGItc) and preparation of nonwovens based on PGItc gels and polylactide. PGItc gels were synthesized by a reaction between itaconic anhydride and glycerol. The use of a mixture of PGItc and PLA allowed us to obtain a material with different properties than with stand-alone polymers. In this study, we present the influence of the chosen ratios of polymers and the OH/COOH ratio in the synthesized PGItc on the properties of the obtained materials. The addition of PGItc results in hydrophilization of the nonwovens' surface without disrupting the high porosity of the fibrous structure. Spectral and thermal analyzes are presented, along with SEM imagining. The preliminary cytotoxicity research showed that nonwovens were non-cytotoxic materials. It also helped to pre-determine the potential application of PGItc + PLA nonwovens as subcutaneous tissue fillers or drug delivery systems. [ABSTRACT FROM AUTHOR]

Dermal fillers have gained significant attention in the field of aesthetic medicine due to their ability to restore volume and correct facial wrinkles. Even though such formulations have similar compositions, they can have different microstructure and molecular characteristics, which in turn affect the biodegradation profile. This study presents the results of an investigation of the physicochemical characteristics of four dermal fillers from different manufacturers (Sculptra®, Gana V®, AestheFill®, and Repart PLA®). The molecular and supramolecular characteristics of polylactic acid (L/D isomer ratio, molecular weight, degree of crystallinity), the morphology and size of PLA microparticles were determined. Hydrolytic degradation studies in phosphate buffer revealed differences in the rate of molecular weight reduction in the polymer. The obtained data may be important for the analysis and interpretation of the results of biological studies and clinical outcomes of the PLA dermal fillers. [ABSTRACT FROM AUTHOR]

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The combination of biocompatibility, biodegradability, and high mechanical strength has provided a steady growth in interest in the synthesis and application of lactic acid-based polyesters for the creation of implants. On the other hand, the hydrophobicity of polylactide limits the possibilities of its use in biomedical fields. The ring-opening polymerization of L-lactide, catalyzed by tin (II) 2-ethylhexanoate in the presence of 2,2-bis(hydroxymethyl)propionic acid, and an ester of polyethylene glycol monomethyl ester and 2,2-bis(hydroxymethyl)propionic acid accompanied by the introduction of a pool of hydrophilic groups, that reduce the contact angle, were considered. The structures of the synthesized amphiphilic branched pegylated copolylactides were characterized by 1H NMR spectroscopy and gel permeation chromatography. The resulting amphiphilic copolylactides, with a narrow MWD (1.14–1.22) and molecular weight of 5000–13,000, were used to prepare interpolymer mixtures with PLLA. Already, with the introduction of 10 wt% branched pegylated copolylactides, PLLA-based films had reduced brittleness, hydrophilicity, with a water contact angle of 71.9–88.5°, and increased water absorption. An additional decrease in the water contact angle, of 66.1°, was achieved by filling the mixed polylactide films with 20 wt% hydroxyapatite, which also led to a moderate decrease in strength and ultimate tensile elongation. At the same time, the PLLA modification did not have a significant effect on the melting point and the glass transition temperature; however, the filling with hydroxyapatite increased the thermal stability. [ABSTRACT FROM AUTHOR]