Biodegradable nanofibers are extensively employed in different areas of biology and medicine, particularly in tissue engineering. The electrospun polycaprolactone (PCL) nanofibers are attracting ...growing interest due to their good mechanical properties and a low-cost structure similar to the extracellular matrix. However, the unmodified PCL nanofibers exhibit an inert surface, hindering cell adhesion and negatively affecting their further fate. The employment of PCL nanofibrous scaffolds for wound healing requires a certain modification of the PCL surface. In this work, the morphology of PCL nanofibers is optimized by the careful tuning of electrospinning parameters. It is shown that the modification of the PCL nanofibers with the COOH plasma polymers and the subsequent binding of NH
groups of protein molecules is a rather simple and technologically accessible procedure allowing the adhesion, early spreading, and growth of human fibroblasts to be boosted. The behavior of fibroblasts on the modified PCL surface was found to be very different when compared to the previously studied cultivation of mesenchymal stem cells on the PCL nanofibrous meshes. It is demonstrated by X-ray photoelectron spectroscopy (XPS) that the freeze-thawed platelet-rich plasma (PRP) immobilization can be performed via covalent and non-covalent bonding and that it does not affect biological activity. The covalently bound components of PRP considerably reduce the fibroblast apoptosis and increase the cell proliferation in comparison to the unmodified PCL nanofibers or the PCL nanofibers with non-covalent bonding of PRP. The reported research findings reveal the potential of PCL matrices for application in tissue engineering, while the plasma modification with COOH groups and their subsequent covalent binding with proteins expand this potential even further. The use of such matrices with covalently immobilized PRP for wound healing leads to prolonged biological activity of the immobilized molecules and protects these biomolecules from the aggressive media of the wound.
•Functional plasma polymer was prepared on electrospun polymer nanofibrous mat.•Plasma polymerization run at atmospheric pressure in Ar/maleic anhydride/C2H2 mixture.•Anhydride/carboxyl plasma ...polymer thin films coated uniformly the polymer nanofibers.•The coating penetrated deep into the nanofibrous mat.
This work investigates for the first time the penetration depth, nanoscopic homogeneity and conformality of the plasma polymerization onto an electrospun nanofibrous mat. The study is carried out on the model example of atmospheric pressure plasma co-polymerization of anhydride-rich films onto polycaprolactone mats that can find a significant practical applications, for example in tissue engineering and regenerative medicine. Since the surface-to-volume ratio of nanofibrous mats is enormous and the structure of mats resembles extracellular matrix the successful plasma coating of each whole fiber and understanding the penetration of the polymerization into the mat structure are extremely important. The films with reactive anhydride groups were prepared by co-polymerization of maleic anhydride and acetylene using dielectric barrier discharge. The studies were accompanied by the quantification of anhydride groups directly on the PCL electrospun mat using the chemical derivatization with trifluoroethylamine and X-ray photoelectron spectroscopy. The nanoscopic homogeneity and conformality of the anhydride plasma polymer coating on the front side and backside of the nanofibrous mat, 30–40 μm in thickness, did not differ according to the dynamic SIMS mapping. The films containing approximately 6 anhydride groups per 100 carbon atoms coated homogeneously the nanofibers deeper in the PCL mat. The characteristic penetration depth of the deposition was estimated as 46 ± 5 μm.
Biodegradable composite nanofibers were electrospun from poly(ε-caprolactone) (PCL) and poly(ethylene oxide) (PEO) mixtures dissolved in acetic and formic acids. The variation of PCL:PEO ...concentration in the polymer blend, from 5:95 to 75:25, revealed the tunability of the hydrolytic stability and mechanical properties of the nanofibrous mats. The degradation rate of PCL/PEO nanofibers can be increased compared to pure PCL, and the mechanical properties can be improved compared to pure PEO. Although PCL and PEO have been previously reported as immiscible, the electrospinning into nanofibers having restricted dimensions (250–450 nm) led to a microscopically mixed PCL/PEO blend. However, the hydrolytic stability and tensile tests revealed the segregation of PCL into few-nanometers-thin fibrils in the PEO matrix of each nanofiber. A synergy phenomenon of increased stiffness appeared for the high concentration of PCL in PCL/PEO nanofibrous mats. The pure PCL and PEO mats had a Young’s modulus of about 12 MPa, but the mats made of high concentration PCL in PCL/PEO solution exhibited 2.5-fold higher values. The increase in the PEO content led to faster degradation of mats in water and up to a 20-fold decrease in the nanofibers’ ductility. The surface of the PCL/PEO nanofibers was functionalized by an amine plasma polymer thin film that is known to increase the hydrophilicity and attach proteins efficiently to the surface. The combination of different PCL/PEO blends and amine plasma polymer coating enabled us to tune the surface functionality, the hydrolytic stability, and the mechanical properties of biodegradable nanofibrous mats.
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•Plasma polymerization penetration depth into porous media is at least tens of μm.•Deposition rate decreases greatly in wells, the chemistry changes moderately.•Two populations of ...film-forming species are required to explain the data.•The small sticking probability population allows the large deposition penetration.
Understanding the role of substrate geometry is vital for a successful optimization of low-pressure plasma polymerization on non-planar substrates used in bioapplications, such as porous materials or well plates. We investigated the altered transport of film-forming species and properties of the coatings for a cyclopropylamine and argon discharge using a combined analysis of the plasma polymer deposition on flat Si pieces, culture wells, microtrenches, a macrocavity, porous hydroxyapatite scaffolds and electrospun polycaprolactone nanofibrous mats. The aspect ratio of the well structures impacted mainly the deposition rate, whereas the film chemistry was affected only moderately. A large deposition penetration depth into the porous media indicated a relatively low sticking probability of film-forming species. A detailed analysis of microtrench step coverage and macrocavity deposition disproved the model of film-forming species with a single overall sticking probability. At least two populations with two different sticking probabilities were required to fit the experimental data. A majority of the film-forming species (76%) has a large sticking probability of 0.20±0.01, while still a significant part (24%) has a relatively small sticking probability of 0.0015±0.0002. The presented methodology is widely applicable for understanding the details of plasma-surface interaction and successful applications of plasma polymerization onto complex substrates.
One of the consequences of the pandemic is a transition to remote education and the use of network audiovisual communication tools for education in musical disciplines. The circumstances of such ...education can differ and might influence the perceived sound or the education. The research observes the ratings of perceived aspects in singing lessons taught in three settings (common, reference, and direct). A variance of several aspects that relate to the perceived sound (temporal qualities and qualities of the sound and room) is observed in the remote forms, suggesting that these can be impaired in some settings and significant in the experience. The findings are discussed in relation to the perceived conditions and present practice.
The scaffolds made of polycaprolactone (PCL) are actively employed in different areas of biology and medicine, especially in tissue engineering. However, the usage of unmodified PCL is significantly ...restricted by the hydrophobicity of its surface, due to the fact that its inert surface hinders the adhesion of cells and the cell interactions on PCL surface. In this work, the surface of PCL nanofibers is modified by Ar/CO₂/C₂H₄ plasma depositing active COOH groups in the amount of 0.57 at % that were later used for the immobilization of platelet-rich plasma (PRP). The modification of PCL nanofibers significantly enhances the viability and proliferation (by hundred times) of human mesenchymal stem cells, and decreases apoptotic cell death to a normal level. According to X-ray photoelectron spectroscopy (XPS), after immobilization of PRP, up to 10.7 at % of nitrogen was incorporated into the nanofibers surface confirming the grafting of proteins. Active proliferation and sustaining the cell viability on nanofibers with immobilized PRP led to an average number of cells of 258 ± 12.9 and 364 ± 34.5 for nanofibers with ionic and covalent bonding of PRP, respectively. Hence, our new method for the modification of PCL nanofibers with PRP opens new possibilities for its application in tissue engineering.
Excellent adhesion of electrospun nanofiber (NF) to textile support is crucial for a broad range of their bioapplications, e.g., wound dressing development. We compared the effect of several low- and ...atmospheric pressure plasma modifications on the adhesion between two parts of composite-polycaprolactone (PCL) nanofibrous mat (functional part) and polypropylene (PP) spunbond fabric (support). The support fabrics were modified before electrospinning by low-pressure plasma oxygen treatment or amine plasma polymer thin film or treated by atmospheric pressure plasma slit jet (PSJ) in argon or argon/nitrogen. The adhesion was evaluated by tensile test and loop test adapted for thin NF mat measurement and the trends obtained by both tests largely agreed. Although all modifications improved the adhesion significantly (at least twice for PSJ treatments), low-pressure oxygen treatment showed to be the most effective as it strengthened adhesion by a factor of six. The adhesion improvement was ascribed to the synergic effect of high treatment homogeneity with the right ratio of surface functional groups and sufficient wettability. The low-pressure modified fabric also stayed long-term hydrophilic (ten months), even though surfaces usually return to a non-wettable state (hydrophobic recovery). In contrast to XPS, highly surface-sensitive water contact angle measurement proved suitable for monitoring subtle surface changes.
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•The XPS derivatization revealed that COOH/COOC ratio for CO2C2H4 plasma polymers does not exceed 0.08.•The attachment of CO2* active species mainly occurs via CO bond leading to the ...formation of ester.•The immersion of CO2C2H4 plasma polymers in water leads to hydrolysis of ester bonds.
The grafting of carboxyl groups enhances cell adhesion and can be used for immobilization of different biomolecules onto plasma-treated materials. The process, however, was not well optimized due to lack of clear understanding of the mechanisms of carboxylic group incorporation into plasma and their grafting to polymer surface. In this work the deposition of COOH plasma polymers from CO2/C2H4/Ar pulsed discharge has been studied depending on the gas mixture and duty cycle. We have demonstrated that the CO2/C2H4/Ar plasma with adjustable thickness of COOH functionalized layer and high stability of the grafted functions in water is a better solution for the COOH surface functionalization compared to the thoroughly analyzed CO2 plasma. The concentration of different carbon environments and the density of COOH groups have been measured by using chemical derivatization combined with X-ray photoelectron spectroscopy. It has been found that the CO2/C2H4/Ar plasma mainly contains ester groups (COOC), the COOH/COOC ratio being between 0.03 and 0.08. The water stability of the COOH groups was significantly higher compared to ester environment, so immersing in water for 24 h allowed to increase the COOH/COOC ratio by a factor of 3. The mechanisms of the CO2 molecule attachment to hydrocarbon chains on the polymer surface and those located inside the plasma were modeled using ab initio calculations.
In somatotroph pituitary tumours, somatostatin analogue (SSA) therapy outcomes vary throughout the studies. We performed an analysis of cohort of patients with acromegaly from the Czech registry to ...identify new prognostic and predictive factors. Clinical data of patients were collected, and complex immunohistochemical assessment of tumour samples was performed (SSTR1‐5, dopamine D2 receptor, E‐cadherin, AIP). The study included 110 patients. In 31, SSA treatment outcome was evaluated. Sparsely granulated tumours (SGST) differed from the other subtypes in expression of SSTR2A, SSTR3, SSTR5 and E‐cadherin and occurred more often in young. No other clinical differences were observed. Trouillas grading system showed association with age, tumour size and SSTR2A expression. Factors significantly associated with SSA treatment outcome included age, IGF1 levels, tumour size and expression of E‐cadherin and SSTR2A. In the group of SGST, poor SSA response was observed in younger patients with larger tumours, lower levels of SSTR2A and higher Ki67. We observed no relationship with expression of other proteins including AIP. No predictive value of E‐cadherin was observed when tumour subtype was considered. Multiple additional factors apart from SSTR2A expression can predict treatment outcome in patients with acromegaly.
: The treatment of gastroesophageal junction (GEJ) adenocarcinoma consists of either perioperative chemotherapy or preoperative chemoradiotherapy. Radiotherapy (RT) in the neoadjuvant setting is ...associated with a higher probability of resections with negative margins (R0) and better tumor regression rate, which might be enhanced by incrementing RT dose with potential impact on treatment results. This virtual planning study demonstrates the feasibility of increasing the dose to GEJ tumor and involved nodes using PET/CT imaging.
: 16 patients from the chemoradiotherapy arm of the phase II GastroPET study were treated by a prescribed dose of 45.0 Gray (Gy) in 25 fractions. PET/CT was performed before treatment. The prescribed dose was virtually boosted on PET/CT-positive areas to 54.0 Gy by 9 Gy in 5 fractions. Dose-volume histograms (DVH) were compared, and normal tissue complication (NTCP) modeling was performed for both dose schedules.
: DVHs were exceeded in mean heart dose in one case for 45.0 Gy and two cases for 54.0 Gy, peritoneal space volume criterion V
< 195 ccm in three cases for 54.0 Gy and V
< 825 ccm in one case for both dose schedules. The left lung volume of 25 Gy isodose exceeded 10% in most cases for both schedules. The NTCP values for the heart, spine, liver, kidneys and intestines were zero for both schemes. An increase in NTCP value was for lungs (median 3.15% vs. 4.05% for 25 × 1.8 Gy and 25 + 5 × 1.8 Gy, respectively,
= 0.013) and peritoneal space (median values for 25 × 1.8 Gy and 25 + 5 × 1.8 Gy were 3.3% and 14.25%, respectively,
< 0.001).
Boosting PET/CT-positive areas in RT of GEJ tumors is feasible, but prospective trials are needed.
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