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The influence of excimer argon fluoride (ArF) laser cutting of poly(L-lactide) (PLLA) on its physicochemical properties was studied. The samples in the form of micro-bars of the size comparable to the width of typical vascular stents struts were fabricated in order to focus during the analysis on heat-affected zone and surfaces exposed to laser radiation and plasma. The threshold fluence and ablation rate of PLLA were measured. The ablated polymer's surface was analyzed using Scanning Electron Microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR-ATR). The produced microstructures with different laser repetition rates and beam size were analyzed using differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) techniques. It allowed tracking the thermal history changes of PLLA, estimating the fraction of modified polymer within micro-bars, and determining the extent of the polymer degradation by observing the molecular weight changes. In many cases, DSC revealed no significant changes in the material's thermal history; however, GPC showed that each laser fabricated sample has a low molecular weight fraction resulting from multi-pulse exposition of the micro-bar walls to UV irradiation, laser-induced plasma, UV irradiation and heat. Nevertheless, most of the micro-bars preserve their original properties within the vast majority of their volume what gives the potential to use them in biomedical applications after cleaning the components from low molecular weight fragments localized at the cut walls. [ABSTRACT FROM AUTHOR]

The laser-based powder bed fusion of polymers (PBF-LB/P) process often utilizes a blend of powders with varying degrees of degradation. Specifically, for polyamide 12, the traditional reuse schema involves mixing post-processed powder with virgin powder at a predetermined ratio before reintroducing it to the process. Given that only about 15% of the powder is utilized in part production, and powders are refreshed in equal proportions, there arises a challenge with the incremental accumulation of material across build cycles. To mitigate the consumption of fresh powder relative to the actual material usage, this study introduces the incorporation of recycled material into the PBF-LB/P process. This new powder reuse schema is presented for the first time, focusing on the laser sintering process. The characteristics of the recycled powder were evaluated through scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, particle size distribution, and dynamic powder flowability assessments. The findings reveal that waste powders can be effectively reused in PBF-LB/P to produce components with satisfactory mechanical properties, porosity levels, dimensional accuracy, and surface quality., 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 © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The aim of the work was to investigate the effect of non-thermal plasma treatment of an ultra-thin polyethylene terephthalate (PET) film on changes in its physicochemical properties and biodegradability. Plasma treatment using a dielectric barrier discharge plasma reactor was carried out in air at room temperature and atmospheric pressure twice for 5 and 15 min, respectively. It has been shown that pre-treatment of the PET surface with non-thermal atmospheric plasma leads to changes in the physicochemical properties of this polymer. After plasma modification, the films showed a more developed surface compared to the control samples, which may be related to the surface etching and oxidation processes. After a 5-min plasma exposure, PET films were characterized by the highest wettability, i.e., the contact angle decreased by more than twice compared to the untreated samples. The differential scanning calorimetry analysis revealed the influence of plasma pretreatment on crystallinity content and the melt crystallization behavior of PET after soil degradation. The main novelty of the work is the fact that the combined action of two factors (i.e., physical and biological) led to a reduction in the content of the crystalline phase in the tested polymeric material.

Novel tissue regeneration strategies are constantly being developed worldwide. Research on bone regeneration is noteworthy, as many promising new approaches have been documented with novel strategies currently under investigation. Innovative biomaterials that allow the coordinated and well-controlled repair of bone fractures and bone loss are being designed to reduce the need for autologous or allogeneic bone grafts eventually. The current engineering technologies permit the construction of synthetic, complex, biomimetic biomaterials with properties nearly as good as those of natural bone with good biocompatibility. To ensure that all these requirements meet, bioactive molecules are coupled to structural scaffolding constituents to form a final product with the desired physical, chemical, and biological properties. Bioactive molecules that have been used to promote bone regeneration include protein growth factors, peptides, amino acids, hormones, lipids, and flavonoids. Various strategies have been adapted to investigate the coupling of bioactive molecules with scaffolding materials to sustain activity and allow controlled release. The current manuscript is a thorough survey of the strategies that have been exploited for the delivery of biomolecules for bone regeneration purposes, from choosing the bioactive molecule to selecting the optimal strategy to synthesize the scaffold and assessing the advantages and disadvantages of various delivery strategies.

Bacteria are the source of many bioactive compounds, including polymers with various physiological functions and the potential for medical applications. Pyomelanin from Pseudomonas aeruginosa , a nonfermenting Gram-negative bacterium, is a black-brown negatively charged extracellular polymer of homogentisic acid produced during L-tyrosine catabolism. Due to its chemical properties and the presence of active functional groups, pyomelanin is a candidate for the development of new antioxidant, antimicrobial and immunomodulatory formulations. This work aimed to obtain bacterial water-soluble (Pyo sol ), water-insoluble (Pyo insol ) and synthetic (sPyo) pyomelanin variants and characterize their chemical structure, thermosensitivity and biosafety in vitro and in vivo ( Galleria mallonella ). FTIR analysis showed that aromatic ring connections in the polymer chains were dominant in Pyo sol and sPyo, whereas Pyo insol had fewer C ar -C ar links between rings. The differences in chemical structure influence the solubility of various forms of pyomelanins, their thermal stability and biological activity. Pyo sol and Pyo insol showed higher biological safety than sPyo. The obtained results qualify Pyo sol and Pyo insol for evaluation of their antimicrobial, immunomodulatory and proregenerative activities.

The use of injectable biomaterials for cell delivery is a rapidly expanding field which may revolutionize the medical treatments by making them less invasive. However, creating desirable cell carriers poses significant challenges to the clinical implementation of cell-based therapeutics. At the same time, no method has been developed to produce injectable microscaffolds (MSs) from electrospun materials. Here the fabrication of injectable electrospun nanofibers is reported on, which retain their fibrous structure to mimic the extracellular matrix. The laser-assisted micro-scaffold fabrication has produced tens of thousands of MSs in a short time. An efficient attachment of cells to the surface and their proliferation is observed, creating cell-populated MSs. The cytocompatibility assays proved their biocompatibility, safety, and potential as cell carriers. Ex vivo results with the use of bone and cartilage tissues proved that NaOH hydrolyzed and chitosan functionalized MSs are compatible with living tissues and readily populated with cells. Injectability studies of MSs showed a high injectability rate, while at the same time, the force needed to eject the load is no higher than 25 N. In the future, the produced MSs may be studied more in-depth as cell carriers in minimally invasive cell therapies and 3D bioprinting applications., (© 2021 Wiley-VCH GmbH.)

In this research, we synthesize and characterize poly(glycerol sebacate) pre-polymer (pPGS) ( 1 H NMR, FTiR, GPC, and TGA). Nano-hydroxyapatite (HAp) is synthesized using the wet precipitation method. Next, the materials are used to prepare a PGS-based composite with a 25 wt.% addition of HAp. Microporous composites are formed by means of thermally induced phase separation (TIPS) followed by thermal cross-linking (TCL) and salt leaching (SL). The manufactured microporous materials (PGS and PGS/HAp) are then subjected to imaging by means of SEM and µCT for the porous structure characterization. DSC, TGA, and water contact angle measurements are used for further evaluation of the materials. To assess the cytocompatibility and biological potential of PGS-based composites, preosteoblasts and differentiated hFOB 1.19 osteoblasts are employed as in vitro models. Apart from the cytocompatibility, the scaffolds supported cell adhesion and were readily populated by the hFOB1.19 preosteoblasts. HAp-facilitated scaffolds displayed osteoconductive properties, supporting the terminal differentiation of osteoblasts as indicated by the production of alkaline phosphatase, osteocalcin and osteopontin. Notably, the PGS/HAp scaffolds induced the production of significant amounts of osteoclastogenic cytokines: IL-1β, IL-6 and TNF-α, which induced scaffold remodeling and promoted the reconstruction of bone tissue. Initial biocompatibility tests showed no signs of adverse effects of PGS-based scaffolds toward adult BALB/c mice.

We present a comparison of the influence of the conditioning temperature of microspheres made of medical grade poly(L-lactide) (PLLA) and polylactide with 4 wt % of D-lactide content (PLA) on the thermal and structural properties. The microspheres were fabricated using the solid-in-oil-in-water method for applications in additive manufacturing. The microspheres were annealed below the glass transition temperature (T g ), above T g but below the onset of cold crystallization, and at two temperatures selected from the range of cold crystallization corresponding to the crystallization of the α' and α form of poly(L-lactide), i.e., at 40, 70, 90, and 120 °C, in order to verify the influence of the conditioning temperature on the sinterability of the microspheres set as the sintering window (SW). Based on differential scanning calorimetry measurements, the SWs of the microspheres were evaluated with consideration of the existence of cold crystallization and reorganization of crystal polymorphs. The results indicated that the conditioning temperature influenced the availability and range of the SWs depending on the D-lactide presence. We postulate the need for an individual approach for polylactide powders in determining the SW as a temperature range free of any thermal events. We also characterized other core powder characteristics, such as the residual solvent content, morphology, particle size distribution, powder flowability, and thermal conductivity, as key properties for successful laser sintering. The microspheres were close to spheres, and the size of the microspheres was below 100 µm. The residual solvent content decreased with the increase of the annealing temperature. The thermal conductivities were 0.073 and 0.064 W/mK for PLA and PLLA microspheres, respectively, and this depended on the spherical shape of the microspheres. The wide angle X-ray diffraction (WAXD) studies proved that an increase in the conditioning temperature caused a slight increase in the crystallinity degree for PLLA microspheres and a clear increase in crystallization for the PLA microspheres.

In this research, we prepared foam scaffolds based on poly(l-lactide) (PLLA) and apatite whiskers (HAP) using thermally induced phase separation technique supported by the salt leaching process (TIPS-SL). Using sodium chloride having a size of (a) 150-315 μm, (b) 315-400 μm, and (c) 500-600 μm, three types of foams with different pore sizes have been obtained. Internal structure of the obtained materials has been investigated using SEM as well as μCT. The materials have been studied by means of porosity, density, and compression tests. As the most promising, the composite prepared with salt size of 500-600 μm was prepared also with the l-lysine modified apatite. The osteoblast hFOB 1.19 cell response for the scaffolds was also investigated by means of cell viability, proliferation, adhesion/penetration, and biomineralization. Direct contact cytotoxicity assay showed the cytocompatibility of the scaffolds. All types of foam scaffolds containing HAP whiskers, regardless the pore size or l-lysine modification induced significant stimulatory effect on the cal-cium deposits formation in osteoblasts. The PLLA/HAP scaffolds modified with l-lysine stimulated hFOB 1.19 osteoblasts proliferation. Compared to the scaffolds with smaller pores (150-315 µm and 315-400 µm), the PLLA/HAP foams with large pores (500-600 µm) promoted more effective ad-hesion of osteoblasts to the surface of the biomaterial.

The PRHD@MnFe 2 O 4 binary hybrids have shown a potential for applications in the biomedical field. The polymer cover/shell provides sufficient surface protection of magnetic nanoparticles against adverse effects on the biological systems, e.g., it protects against Fenton's reactions and the generation of highly toxic radicals. The heating ability of the PRHD@MnFe 2 O 4 was measured as a laser optical density (LOD) dependence either for powders as well as nanohybrid dispersions. Dry hybrids exposed to the action of NIR radiation (808 nm) can effectively convert energy into heat that led to the enormous temperature increase Δ T 170 °C (>190 °C). High concentrated colloidal suspensions (5 mg/mL) can generate Δ T of 42 °C (65 °C). Further optimization of the nanohybrids amount and laser parameters provides the possibility of temperature control within a biologically relevant range. Biological interactions of PRHD@MnFe 2 O 4 hybrids were tested using three specific cell lines: macrophages (RAW 264.7), osteosarcoma cells line (UMR-106), and stromal progenitor cells of adipose tissue (ASCs). It was shown that the cell response was strongly dependent on hybrid concentration. Antimicrobial activity of the proposed composites against Escherichia coli and Staphylococcus aureus was confirmed, showing potential in the exploitation of the fabricated materials in this field.

A novel and successful application of ring-closing reactions of aminophenols has been proposed for the formation of a new type of 1,3-benzoxazine ionic derivatives. The optimization of the reaction and detailed computational studies have been reported for the estimation of heterocyclic ring stability and its further transformation, which is crucial in the polymerization process. The molecular structure of the obtained compounds has been fully characterized by applying X-ray analysis and spectroscopic methods. The novel benzoxazines undergo an intriguing thermal reaction leading to classical benzoxazines and chloroalkanes, which is the first step of transformation before polymerization. To gain more insights into the transformation behavior of ionic benzoxazine derivatives, the Fourier transform infrared (FT-IR) spectra of gaseous products were recorded in experiments with near simultaneous FT-IR/TGA measurements. The combination of thermogravimetry with FT-IR spectroscopy enables the quantitative and qualitative characterization of thermal transformation products and clarification of the reaction mechanism. The experimental data have been verified by applying DFT(B3LYP) and DFT(M062x) theoretical studies., Competing Interests: The authors declare no competing financial interest.

Novel biocomposites of poly(L-lactide) (PLLA) and poly(l-lactide-co-glycolide) (PLLGA) with 10 wt.% of surface-modified hydroxyapatite particles, designed for applications in bone tissue engineering, are presented in this paper. The surface of hydroxyapatite (HAP) was modified with polyethylene glycol by using l-lysine as a linker molecule. The modification strategy fulfilled two important goals: improvement of the adhesion between the HAP surface and PLLA and PLLGA matrices, and enhancement of the osteological bioactivity of the composites. The surface modifications of HAP were confirmed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), TGA, and elemental composition analysis. The influence of hydroxyapatite surface functionalization on the thermal and in vitro biological properties of PLLA- and PLLGA-based composites was investigated. Due to HAP modification with polyethylene glycol, the glass transition temperature of PLLA was reduced by about 24.5 °C, and melt and cold crystallization abilities were significantly improved. These achievements were scored based on respective shifting of onset of melt and cold crystallization temperatures and 1.6 times higher melt crystallization enthalpy compared with neat PLLA. The results showed that the surface-modified HAP particles were multifunctional and can act as nucleating agents, plasticizers, and bioactive moieties. Moreover, due to the presented surface modification of HAP, the crystallinity degree of PLLA and PLLGA and the polymorphic form of PLLA, the most important factors affecting mechanical properties and degradation behaviors, can be controlled.

Over the past few years we have witnessed growing interest in ultrafast laser micromachining of bioresorbable polymers for fabrication of medical implants and surface modification. In this paper we show that surface structuring of poly(L-lactide) with 300 fs laser pulses at 515 and 1030 nm wavelength leads to formation of defects inside the polymer as a result of laser beam filamentation. Filament-induced channels have diameter around 1 μm and length of hundreds of micrometers. SEM images of microchannels cross-sections are presented. The influence of wavelength and pulse spacing on bulk modification extent was investigated and parameters limiting filamentation were determined. We show that filamentation can be used for controlling properties of PLLA. The presence of filament-induced modifications such as empty microchannels and pressure wave-induced stress lead to increased ability of polymer to crystallize at lower temperature. Crystallization behaviour and crystal morphology after laser treatment was investigated in details using different analytical techniques such as WAXD, DSC and FTIR/ATR. Hydrolytic degradation experiment was performed. Presented method can be applied for controllable, spatially distributed modification of polymer crystallinity, crystalline phase structure and hydrolytic degradation profile.