The Influence of Soft Segment Structure on the Properties of Polyurethanes.

A series of polyurethanes (PU) were synthesised via one-step polymerisation without a chain extender, using toluene diisocyanate as well as a variety of soft segments composed of different macrodiols. Poly(D,L-lactide) (PDLLA) and polycaprolactone diol (PCL) were synthesised as a polyester type polyols to obtain soft segments. The process of varying the molar ratio of newly synthesised PDLLA in soft segments has been confirmed as a powerful tool for fine-tuning the final properties of PU. Fourier-transformed infrared spectroscopy was used for evaluation of molecular structures of synthesised PDLLA polyol and final PU. Nuclear magnetic resonance spectrometry was used to confirm the presumed structure of PU. The influence of soft segment composition on polyurethane thermal characteristics was examined using thermogravimetric analysis and differential scanning calorimetry. The composition of soft segments had little impact on the thermal stability of PU materials, which is explained by the comparable structures of both polyester polyols. Wide-angle X-ray scattering was utilised to evaluate the effect of amorphous PDLLA on the degree of crystallinity of PCL in soft PU segments. It was discovered that not only did the PDLLA ratio in the soft segment have a substantial influence on the degree of microphase separation in the soft and hard segments, but it also influenced the crystallisation behaviour of the materials. Furthermore, the restriction of crystallisation of the PCL soft segment has been verified to be dependent on the hard segment concentration and the ratio of PDLLA/PCL polyols. The sample with pure PCL as the polyol component achieved the highest degree of crystallinity (34.8%). The results demonstrated that the composition of soft segments directly affected the properties of obtained polyurethane films. These results can be utilised to easily achieve a desirable set of properties required for application in biomaterials.

Temperature-Sensitive Hydrogels as Carriers for Modulated Delivery of Acetaminophen.

The purposes of this study are the polymerization of temperature-sensitive copolymers based on N-isopropyl acrylamide and 10 mol % of 2-hydroxypropylmethacrylate, characterisations of their thermal, morphological and swelling properties, as well as the analysis of potential application in drug-delivery systems. Acetaminophen, the representative of non-steroidal anti-inflammatory drugs, was used as a model drug in this study. It is a common pain relief drug, which is also used for fever treatment. However, oral administration comes with certain health risks, mainly the overdose and frequent administration of up to four times a day. The goal of applying temperature-sensitive hydrogel is to enable extended administration once a day, depending on the body temperature. The swelling behavior of the obtained poly(N-isopropyl acrylamide-co-2-hydroxypropylmethacrylate) (p(NIPA/HPMA)) hydrogels and their temperature-sensitivity, kinetics and order of swelling processes at 18 and 38 °C were analyzed. The thermal properties of these hydrogels were observed by the DSC method, and the obtained thermograms showed both melting and glass transitions. The drug delivery system of p(NIPA/HPMA) hydrogels with loaded acetaminophen was analyzed using scanning electron microscopy and Fourier transform infrared spectroscopy methods. Structural analysis of FTIR spectra indicates that non-covalent intermolecular interactions of the type of hydrogen bonds were formed among functional groups of acetaminophen and side-chains of p(NIPA/HPMA) hydrogels. The surface structure of p(NIPA/HPMA) hydrogels after drug loading indicates the acetaminophen presence into the pores of the hydrogel network, and their loading efficiency was higher than 92%. Qualitative and quantitative analysis of acetaminophen, determined by the high-pressure liquid chromatography method, showed that about 90-99% of the loaded amount was released from p(NIPA/HPMA) hydrogels within 24 h. Kinetic parameters of the acetaminophen release under simulated gastrointestinal conditions were determined. Based on obtained results, the drug delivery system of temperature-sensitive p(NIPA/HPMA) hydrogels with loaded acetaminophen could be suitable for additional investigation for modulated drug administration, e.g., for extended drug administration.

A Review of Patents and Innovative Biopolymer-Based Hydrogels.

Biopolymers represent a great resource for the development and utilization of new functional materials due to their particular advantages such as biocompatibility, biodegradability and non-toxicity. "Intelligent gels" sensitive to different stimuli (temperature, pH, ionic strength) have different applications in many industries (e.g., pharmacy, biomedicine, food). This review summarizes the research efforts presented in the patent and non-patent literature. A discussion was conducted regarding biopolymer-based hydrogels such as natural proteins (i.e., fibrin, silk fibroin, collagen, keratin, gelatin) and polysaccharides (i.e., chitosan, hyaluronic acid, cellulose, carrageenan, alginate). In this analysis, the latest advances in the modification and characterization of advanced biopolymeric formulations and their state-of-the-art administration in drug delivery, wound healing, tissue engineering and regenerative medicine were addressed.

Development of Light-Polymerized Dental Composite Resin Reinforced with Electrospun Polyamide Layers.

As the mechanical properties of resin-based dental composite materials are highly relevant in clinical practice, diverse strategies for their potential enhancement have been proposed in the extant literature, aiming to facilitate their reliable use in dental medicine. In this context, the focus is primarily given to the mechanical properties with the greatest influence on clinical success, i.e., the longevity of the filling in the patient's mouth and its ability to withstand very strong masticatory forces. Guided by these objectives, the goal of the present study was to ascertain whether the reinforcement of dental composite resins with electrospun polyamide (PA) nanofibers would improve the mechanical strength of dental restoration materials. For this purpose, light-cure dental composite resins were interspersed with one and two layers comprising PA nanofibers in order to investigate the influence of such reinforcement on the mechanical properties of the resulting hybrid resins. One set of the obtained samples was investigated as prepared, while another set was immersed in artificial saliva for 14 days and was subsequently subjected to the same set of analyses, namely Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). Findings yielded by the FTIR analysis confirmed the structure of the produced dental composite resin material. They also provided evidence that, while the presence of PA nanofibers did not influence the curing process, it strengthened the dental composite resin. Moreover, flexural strength measurements revealed that the inclusion of a 16 µm-thick PA nanolayer enabled the dental composite resin to withstand a load of 3.2 MPa. These findings were supported by the SEM results, which further indicated that immersing the resin in saline solution resulted in a more compact composite material structure. Finally, DSC results indicated that as-prepared as well as saline-treated reinforced samples had a lower glass transition temperature (Tg) compared to pure resin. Specifically, while pure resin had a Tg of 61.6 °C, each additional PA nanolayer decreased the Tg by about 2 °C, while the further reduction was obtained when samples were immersed in saline for 14 days. These results show that electrospinning is a facile method for producing different nanofibers that can be incorporated into resin-based dental composite materials to modify their mechanical properties. Moreover, while their inclusion strengthens the resin-based dental composite materials, it does not affect the course and outcome of the polymerization reaction, which is an important factor for their use in clinical practice.

Biomedical Applications of Thermosensitive Hydrogels for Controlled/Modulated Piroxicam Delivery.

The objectives of this study are the synthesis of thermosensitive poly(N-isopropylacrylamide-co-2-hydroxypropyl methacrylate), p(NiPAm-HPMet), hydrogels and the analysis of a drug-delivery system based on piroxicam, as a model drug, and synthesized hydrogels. A high pressure liquid chromatography method has been used in order to determine both qualitative and quantitative amounts of unreacted monomers and crosslinkers from polymerized hydrogels. Swelling kinetics and the order of a swelling process of the hydrogels have been analyzed at 10 and 40 °C. The copolymers' thermal properties have been monitored by the differential scanning calorimetry (DSC) method. DSC termograms have shown that melting occurs in two temperature intervals (142.36-150.72 °C and 153.14-156.49 °C). A matrix system with incorporated piroxicam has been analyzed by using FTIR and SEM methods. Structural analysis has demonstrated that intermolecular non-covalent interactions have been built between side-groups of copolymer and loaded piroxicam. Morphology of p(NiPAm-HPMet) after drug incorporation indicates the piroxicam presence into the copolymer pores. Kinetic parameters of the piroxicam release from hydrogels at 37 °C and pH 7.4 indicate that the fluid transport mechanism corresponds to Fickian diffusion. As a result, formulation of thermosensitive p(NiPAm-HPMet) hydrogels with incorporated piroxicam could be of interest for further testing as a drug carrier for modulated and prolonged release, especially for topical administration.

Fast Fourier transform IR characterization of epoxy GY systems crosslinked with aliphatic and cycloaliphatic EH polyamine adducts.

The use of fast FT-IR spectroscopy as a sensitive method to estimate a change of the crosslinking kinetics of epoxy resin with polyamine adducts is described in this study. A new epoxy formulation based on the use of polyamine adducts as the hardeners was analyzed. Crosslinking reactions of the different stoichiometric mixtures of the unmodified GY250 epoxy resin with the aliphatic EH606 and the cycloaliphatic EH637 polyamine adducts were studied using mid FT-IR spectroscopic techniques. As the crosslinking proceeded, the primary amine groups in polyamine adduct are converted to secondary and the tertiary amines. The decrease in the IR band intensity of epoxy groups at about 915 cm(-1), as well as at about 3,056 cm(-1), was observed due to process. Mid IR spectral analysis was used to calculate the content of the epoxy groups as a function of crosslinking time and the crosslinking degree of resin. The amount of all the epoxy species was estimated from IR spectra to changes during the crosslinking kinetics of epichlorhydrin.

Physical-Mechanical Properties of Nitrodopes Affected by Ultra-Violet Radiation.

The FTIR spectroscopy has been employed in this research work to monitor theprocess of nitrodope photodegradation, by measuring surfaces of bands typical of a nitrogroup. Nitric esters are subject to degradation, which is reflected on a quantitative ratio ofthe surfaces of the IR bands that originate from the nitric ester. The obtained results showthat the length of the UV rays' activity on the samples over the time periods of 240, 480and 960 minutes directly affects the spectrum appearance of the same sample before andafter the irradiation. The longer the action time of the UV rays and the higher a masspercentage of nitrocellulose in the nitrodope is, the smaller the bands' surfaces become, i.e.the level of degradation is higher. In order to confirm the degradation of nitrodope, thedegree of crosslinking has also been examined by determining the König hardness and alsothe mean viscosity molar mass has been defined repeatedly applying the capillaryviscosimetry method.