Dokonano syntezy poliuretanu w reakcji 4,4'-di-izocyjanianu dicykloheksylometylenu (HMDI), poli(e-kaprolaktono)diolu (PKL) i butano-1,4-diolu w roztworze dioksanu, w którym zdyspergowano cząstki krzemionki. Metodą SEM-EDX oceniono równomierność rozmieszczenia cząstek nanonapełniacza w matrycy polimerowej. Metodami DSC i WAXD wykazano obecność fazy uporządkowanej zdyspergowanej wraz z nanocząstkami krzemionki w matrycy poliuretanu. Oceniono wpływ krzemionki na wzrost wytrzymałości mechanicznej i termicznej otrzymanych nanokompozytów uformowanych w postaci cienkich powłok. Na podstawie pomiarów kątów zwilżania oraz wartości swobodnej energii powierzchniowej stwierdzono wzrost charakteru hydrofilowego otrzymanych powłok.
EN
A polyurethane was synthesized by reaction of dicycloheksylmethylene 4,4'-diisocyanate, poly(caprolactone)diol and butane-1,4-diol in dioxane with dispersed nano SiO₂. Distribution of nano SiO₂ in polymer matrix was examd. by SEM-EDX method. The presence of ordered dispersed phase in the polyurethane matrix was showed by DSC and WAXD methods. The addn. of SiO2 resulted in an increase of mech. strength, and thermal properties of the coatings. The hydrophilic nature of the coatings was evidenced by contact angles and surface free energy measurements.
Microspheres (MS) made of resorbable polymer have been proposed as a cell growth support. They may be assembled to form cell constructs or be suspended in hydrogels allowing injection into injury location. High relative surface area of MS provides more efficient cell culture environment than traditional culture on flat substrates (multiwell plates, Petri dishes). In addition, MS structure, topography and surface chemistry can be modified to promote cell adhesion and proliferation. The aim of this study was to obtain resorbable poly(L-lactide-co-glycolide) (PLGA) MS and to modify their properties by changing manufacturing conditions of the oil-in-water emulsification to better control structural and microstructural properties of MS and their biological performance. To this end, water phase was modified by addition of NaCl to change ionic strength, while oil phase by addition of polyethylene glycol (PEG). Microstructural and thermal properties were assessed. Cytocompatibility tests and cell cultures with MG-63 cells were conducted to verify potential relevance of MS as cell carriers. The results showed that it is possible to obtain cytocompatible MS by oil-in-water emulsification method and to control diameter, porosity and crystallinity of MS with the use of additives to oil and/or water phases without negative changes in MS cytocompatibility. The results prove that modification of both phases make it possible to produce MS with desired/controllable properties like surface topography, porosity and crystallinity.
Kompozyty poliuretanowe otrzymywano w reakcji diizocyjanianu HDI lub HMDI, poli(kaprolaktono)diolu i 1,4-butanodiolu w roztworze 1,4-dioksanu, zawierającym zdyspergowany hydroksyapatyt. Metodami SEM iEDX oceniono stopień rozproszenia cząstek nanonapełniacza w matrycy poliuretanowej, a technikami DSC, DSC TOPEM i WAXD zbadano właściwości termiczne i określono wpływ hydroksyapatytu na zdolność do krystalizacji poliuretanu liniowego, uformowanego w postaci cienkiej powłoki. Ze względu na możliwość zastosowania otrzymanego kompozytu jako biomateriału oznaczono jego właściwości mechaniczne, określono charakter chemiczny otrzymanej powłoki i jej odporność hydrolityczną podczas długotrwałej inkubacji w płynie fizjologicznym.
EN
Polyurethane composites were obtained in the reaction of HDI or HMDI diisocyanate, polycaprolactone diol and 1,4-butanediol in 1,4-dioxane solution containing dispersed hydroxyapatite. The distribution of hydroxyapatite particles in the polymer matrix has been examined using SEM-EDX method. By applying DSC, TOPEM DSC and WAXD methods the thermal properties and effect of hydroxyapatite on the crystallization ability of linear polyurethane in the form of thin film have been investigated. With regard to the possibility of using the obtained composite as a biomaterial its mechanical and thermal properties have been determined. Also, the chemical character of the obtained coating and its hydrolytic resistance during long-term incubation in physiological fluid have been evaluated.
PU elastomers were synthesized using MDI, PTMO, butane-1,4-diol or 2,2,3,3-tetrafiuorobutane-1,4-diol. Using the same diisocyanate and polyether reagents urethane segments were prepared, to be inserted in the poly(urethane-methacrylate) copolymers. Bromourethane or tetraphenylethane-urethane macroinitiators were used as transitional products reacting with MMA according to the ARGET ATRP. 1H and 13C NMR spectral methods, as well as DSC and TGA thermal methods, were employed to confirm chemical structures of synthesised elastomers and copolymers. To investigate the possibility of using synthesized polymers as biomaterials a research on keeping them in physiological liquid at 37°C was performed. A loss in weight and ability to sorption of water was determined and by using GPC the molecular weight changes were compared. Additionally, changes in the thermal properties of the samples after exposure in physiological liquid were documented using both the TGA and DSC methods. The studies of surface properties (confocal microscopy and SFE) of the obtained polymers were performed. The structure of the polymer chains was defined by NMR. Possible reasons of hydrolysis were discussed, stating that new copolymers are more resistant and polar biomaterials can be less interesting than elastomers.
Celem przeprowadzonych badań było uzyskanie nowego wielofunkcyjnego biomateriału do regeneracji tkanki kostnej, spełniającego wymagania stawiane przez nowe trendy w medycynie regeneracyjnej. Biorąc pod uwagę wymagania związane ze zgodnością biologiczną oraz minimalną szkodliwością implantu dla organizmu ludzkiego, z grupy dostępnych naturalnych i syntetycznych polimerów jako najbardziej obiecujący wybrany został chitozan. Chitozan jest coraz częściej używanym polimerem w zastosowaniach medycznych, takich jak: opatrunki, systemy dostarczania leku, system dostarczania genów, podłoża do regeneracji kości i tkanek miękkich, itp. Istotną zaletą chitozanu jest jego zdolność do tworzenia fazy hydrożelowej i ta właściwość jest wykorzystywana przez naukowców do uzyskiwania nowych biomateriałów. Obecnie hydrożele są używane w zastosowaniach sensorycznych wykorzystujących sygnały temperaturowe, pH, siły jonowej, jonowe czy przyłożonego zewnętrznego pola magnetycznego do wywołania oczekiwanej odpowiedzi. W niniejszej pracy został zastosowany syntetyczny nanokrzemian warstwowy pod nazwą handlową Laponite® XLS zamiast powszechnie stosowanych organicznych środków sieciujących często szkodliwych dla pacjenta. Uzyskane próbki zostały scharakteryzowane za pomocą różnicowej kalorymetrii skaningowej (DSC), spektroskopii w podczerwieni z transformacją Fouriera (FT-IR), dyfrakcji rentgenowskiej oraz testu nasiąkliwości. Do wstępnego określenia bioaktywności materiałów zastosowano test w warunkach in vitro zaproponowany przez Kokubo. Uzyskane dane poddane ocenie i szczegółowej analizie dały pozytywne i obiecujące wyniki.
EN
The aim of the study was to obtain novel multifunctional biomaterials for bone tissue regeneration fulfilling the requirements imposed by new trends in regenerative medicine. Taking into account that implant has to be biocompatible and less harmful to humans, from a group of available natural and synthetic polymers chitosan was chosen as one of the most promising biomaterials. Chitosan is more and more commonly used in medicine for wound dressings, drug delivery systems, gene delivery systems, scaffolds for bone and soft tissue regeneration etc. Important advantage of chitosan is its ability to create hydrogel phases and this property is used by scientists to obtain novel biomaterials. Nowadays hydrogels are commonly used in sensing applications using temperature, pH, ions, ionic strength or external magnetic field mechanisms to trigger the desired response. Having regarded patient care, synthetic nanoclay (trade name Laponite® XLS) was applied instead of commonly used organic cross--linkers. Obtained specimens were characterized by differential scanning calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction and water soaking test. The in vitro test proposed by Kokubo was performed to determine bioactivity of the materials. Obtained data were analyzed in detail and provided positive and promising information.
Biodegradable materials for drug delivery and bone tissue engineering are currently intensively developing and improving, but there are still a lot of problems to solve related with bioactivity, biocompatibility, release profile etc. Osteosarcoma is an aggressive malignant neoplasm arising from primitive transformed cells of mesenchymal origin that exhibit osteoblastic differentiation and produce malignant osteoid. It is the most common histological form of primary bone cancer [1,2]. Treatment is most destinations and made up for: intensive multidrug short induction chemotherapy, amputation or tumor resection within the limits of normal tissue and in the last phase again chemotherapy. This kind of neoplasm is most recently detected in young male till 25 age, therefore improving methods of treatment is so important. Chitosan is a natural-based polymer obtained by alkaline deacetylation of chitin received from powdered shrimp shells was purchased from Acros Organics. Its main advantages are non-toxic, non-immunogenic, non-carcinogenic degradation products, biocompatible, bioactive and biodegradable. These properties cause chitosan a very good candidate for novel hydrogel drug delivery systems. Chitosan easily forms hydrogel particles and entraps biomolecules through a number of mechanisms, including chemical crosslinking, ionic crosslinking, and ionic complexation [3,4]. A possible alternative of chitosan by the chemical modification also has been useful for the association of bioactive molecules to polymer and controlling the drug release profile. There are few methods of modification, or example.: copolimerization, grafting, chemical and ionic crosslinking, polyelectrolyte complexes, etc [5]. Previous studies demonstrated that chitosan could promote the proliferation and osteogenesis but only with moderate swelling ratio of composite, too high ability of entrapment water solutions are not recommended. There are a lot of advantages in chitosan properties that can be used in research work to obtain the material of the best expected properties. Laponite® (LA) is a plate-like synthetic clay hectoritetype belongs to a family of phyllosolicates type 2:1 [6]. Its structure represent empirical formula: Na0.7+[Si8Mg5.5Li0.3 O20(OH)4]0.7-. The plates size is about 25 nm x 0,92 nm. LA has a large surface area, anionic surface charges and exchangeable Na+ cations in hydrated interlayers. Presence of sodium cations causes better adsorption properties for cationic drug molecules. Moreover, the exfoliated LA particles may act as multifunctional crosslinkers in forming the nanocomposite hydrogels, and the polymer chains were anchored to the particles and entangled to form a network [7]. Used synthetic clay has got the same type structure and but better sorption properties to montmorillonite but it has got serious advantage - as a synthetic compound shows low heavy metal content. The initial results indicate that the incorporation of clay improved the swelling behavior in contrast to the pure chitosan beads. There also had been revealed significant disproportion of viscosity received hydrogels according to different type of LA or different concentration. Increasing content causes telling rise of viscosity, especially reported in higher content of used crosslinker. The aim of research is to develop a bioactive system biopolymer/layered silicate intelligent nanocomposite based on chitosan and synthetic clay by a cross-linking reaction using sodium tripolyphosphate as the gel factor. The resultant composite were characterized by Fourier transform infrared spectroscopy, scanning electronic microscope and X-ray diffraction analysis. The bioactivity in physiological pH solution (SBF pH=7.40) [8], drug encapsulation efficiency and controlled release behaviour were also investigated by using the model drug to reveal the effects of introduced LA.