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EN
When designing injectable scaffolds for biomedical applications, it is crucial to determine the conditions for the formation of unlimited structures, in particular the kinetics at constant temperature. Despite many studies, these conditions have not been characterized so far after injection, which is such an important application aspect. The aim of the research is to discuss the impact of the injection application on the polymer structure and to propose new criteria for assessing the potential of thermosensitive biopolymer sols, considering the flow under high shear rates during the administration. Based on the analysis of the obtained results of rheological tests, it was shown that the flow through the needles causes a significant change in the elastic properties that define the polymer structure, with almost unchanged viscous properties. As a consequence, the parameters characterizing the polymer coil change, which, combined with the quantitatively proven fragmentation, indicates that injection application may affect the size of the coils that will not reach the critical size of the aggregating nucleus. Finally, extended research procedures for the conscious design of injectable scaffolds are proposed as well as key rheological parameters to ensure thermoinduced aggregation preceded by shear during injection are provided.
EN
This paper discusses the influence of the direction of applied deformation on the ability to gelation of thermosensitive chitosan hydrogels. The application of the shear rate equal in value to the classically performed oscillatory measurements leads to significantly different shapes of experimental curves. It was found that the type of mechanically applied deformation has a significant impact on the gelation ability of colloidal chitosan solutions and conditions of sol-gel phase transition. Simple shear leads to a phase transition at a lower temperature or in a shorter time compared to oscillatory tests. Moreover, based on the final values of dynamic viscosity in rotational measurements, it was found that stronger crosslinking of the polymer structure was observed.
EN
The thermosensitive hydrogels are widely used in tissue engineering due to their non-invasive application. Special interest of researchers, due to the specific characteristics of both materials, is aimed at composites of natural origin obtained from chitosan hydrogels combined with collagen. The mechanical properties of the thermosensitive chitosan-fish collagen hydrogels and the sol-gel phase transition parameters were determined by the rotational rheometry measurement techniques. Based on comparison of the obtained storage modulus G' curves, it was found that the addition of collagen negatively affects the mechanical properties of composite scaffolds. The addition of this protein substance decreases their elasticity. Only the smallest concentration (0.25g collagen/1 g chitosan) of collagen improves the mechanical properties of composite hydrogels, from 56 kPa to 61 kPa. Conducted non-isothermal studies allowed to conclude that the addition of collagen causes an increasing temperature of sol-gel phase transition. However, the observed changes are not a monotone function of the biopolymer concentration.
PL
W pracy przedstawiono wyniki badań reologicznych roztworów chlorku chitozanu formujących żele pod wpływem wzrostu temperatury. Miały one na celu wyznaczenie podstawowych parametrów określających przemianę fazową: temperaturę żelowania oraz energię potrzebną do przeprowadzenia tej przemiany. Prace te są istotne z uwagi na możliwość zastosowania takich układów jako skafoldów do hodowli komórkowej bądź nośników leków umożliwiających ich wprowadzanie do tkanki zmienionej chorobowo drogą iniekcji. Badania wykonano dla chitozanów o różnym pochodzeniu: crab, shrimp i różnej masie cząsteczkowej. Dla każdego z chitozanów przeprowadzono badania roztworów chlorku chitozanu bez oraz z dodatkiem disodowej soli β-glicerofosforanu (β-NaGP). Punkt przemiany fazowej wyznaczano za pomocą pomiarów zmian właściwości reologicznych prowadzonych w układzie stożek-płytka reometru rotacyjnego. Ponadto wyznaczono zmiany wartości pH roztworów oraz zmianę modułów: zachowawczego G’ i stratności G’’ w funkcji przyrostu temperatury. Na podstawie wyników pomiarów stwierdzono istotny wpływ pH na temperaturę punktu żelowania. Przeprowadzone pomiary reologiczne pozwoliły wyznaczyć trzy charakterystyczne obszary procesu żelowania: (1) obszar cieczy lepkosprężystej, (2) obszar szybkiego żelowania, (3) obszar wolnego procesu żelowania oraz określić, w oparciu o model kinetyki krystalizacji polimeru, energię aktywacji dla obszarów 2 i 3.
EN
The paper presents the results of rheological study on chitosan chloride solutions, forming gels under the influence of increased temperature. Its aim was to establish the basic parameters specifying phase transition: gelation temperature and the energy needed for conducting this transition. This study is significant due to the possibility of applying such systems as scaffolds for tissue engineering or drug delivery systems. The research was conducted for chitosans of various origin: crab, shrimp and of various molecular weights. For each chitosan, research was conducted in two variations of the solutions of chitosan chloride, with or without the addition of β-Glycerophosphate disodium salt (β-NaGP). The phase transition point was estimated by measurements of rheological properties, conducted in a cone-plate system of a rotational rheometer. Moreover, the pH value of the solutions and the evolution of storage modulus G’ and loss modulus G’’ in the function of temperature increase were determined. Based on the measurements results a significant impact of pH on the gelation point temperature was observed. The conducted rheological measurements allowed to estimate three characteristic regions of the gelation process: (1) area of viscoelastic liquid, (2) area of fast gelation, (3) area of a slow gelation process. Based on the kinetics model of polymer crystallization, the activation energy for regions 2 and 3 was determined.
PL
W pracy zaprezentowano metodę wyznaczania temperatury punktu przemiany fazowej zol-żel roztworów soli chitozanowych wykorzystującą pomiary zmian potencjału zeta. Otrzymane wyniki porównano z pomiarami zmian właściwości Teologicznych podczas przemiany fazowej wywołanej zmianą temperatury. Pomiary potencjału zeta w zakresie przemian w fazie ciekłej dobrze opisują występujące zjawiska. W obszarze tworzenia się żelu, pomiary te obarczone są błędem wynikającym z morfologii próbki.
EN
A method to determine the temperature of sol-gel phase transition of the chitosan salt solution based on measurements of zeta potential is presented. The results are compared with measurements of the rheological properties of phase transition under effect of temperature increase. Measurements of zeta potential in the range of sol phase are in accuracy with the investigated phenomenon. In the range of gel formation, the errors of experimental data result from the sample morphology.
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