Andrzej Swinarew

The Evaluation of Long-Term Aged PVC

The article presents the impact of long-term (10 years of maintenance) use of polymer material, with the result of a gradual loss of primary physical and chemical properties and degradation. Under the influence of factors such as heat, water, sunlight, stress forces, sulfur oxides, nitrogen oxides, oxygen, metals, and microorganisms, polymers experience irreversible structural changes that cause a decrease in molecular weight or change in chemical composition. The problems mentioned in this article are known worldwide because of many possible applications for wide-area covers, roofing and others.

Ring-Opening Polymerization of Lactones Initiated with Metal Hydroxide-Activated Macrocyclic Ligands: Determination of Mechanism and Structure of Polymers

Anhydrous alkali metal hydroxide (KOH, NaOH, and LiOH)-activated macrocyclic ligand complexing metal cations, i.e., coronands 12C4, 15C5, 18C6, DCH24C8, and cryptand C222, were selected for initiation of β-butyrolactone (β-BL) and ε-caprolactone (ε-CL) polymerization. It was found that β-BL polymerizes in the presence of KOH/18C6, KOH/C222, and NaOH/C222 systems. The real initiators in this case are two salts, potassium 3-hydroxybutyrate and potassium trans-crotonate, which are responsible for the formation of two fractions of the obtained polymer. ε-CL underwent polymerization with KOH or NaOH activated by all ligands used or without the ligand but with LiOH/12C4. Using KOH-activated strong ligands, i.e., 15C5, 18C6, or C222, two polymer fractions were generated containing linear and, unexpectedly, also cyclic macromolecules. The mechanism of the studied processes is discussed.

Induction of Apoptosis in Normal Human Dermal Fibroblasts Infected with Borrelia burgdorferi Sensu Lato

The spirochete Borrelia burgdorferi s.l. can enter into different eukaryotic cells. Intracellular localization of bacteria may cause many changes in different cell pathways like apoptosis-mediated caspase cascade. The present studies focused on gene expression associated with caspase cascade after normal human dermal fibroblasts (NHDF) infection with Borrelia garinii, Borrelia afzelii, and B. burgdorferi s.s. The use of oligonucleotide microarray technique enabled an expression level comparison of genes associated with caspase cascade in NHDF infected with spirochetes. The increased expression of genes associated with caspase cascade was observed in case of CASP5, CASP2, CARD10, CASP10, MALT1, and NLRP1. The decreased expression was observed in case of CASP4, CASP6, and CASP1. The mRNA expression for CASP3 was inhibited in cells infected with three genospecies of Borrelia. However, the intensity of fluorescence was not statistically significant. In addition, cell cultures were fixed and procedure of caspase-3 detection and the TUNEL assay were performed. The in situ caspase-3 detection procedure confirmed the results obtained from microarray analyses. Only several fluorescent signals were observed. Many apoptotic cells were detected in NHDF-infected cultures with all spirochete genospecies found using the TUNEL reaction.

The Influence of Crown Ether and Alcohol on Unsaturation and Molar Mass of Poly(propylene oxide)s Prepared by Use of Potassium t-Butoxide: Reinvestigation of Chain Transfer Reactions

Potassium t-butoxide dissolved in tetrahydrofuran effectively initiates homogeneous polymerization of propylene oxide at room temperature. Unsaturation and molar mass (M n) of the polymers prepared depend on the presence of additives, such as macrocyclic ligand 18-crown-6 (L) and t-butanol. Application of the ligand alone results in distinct increase of unsaturation and decrease of M n, whereas use of t-BuOH leads to simultaneous decrease of unsaturation and M n. Activation of t-BuOK/t-BuOH system with the ligand causes further decrease of unsaturation, that is, from 12.0 to 3.5 mol % for OK/OH (1/3) and OK/OH/L (1/3/2) systems, respectively. Unexpectedly, M n of the polymers obtained does not practically change (~4800). This result differs from that reported earlier for neat PO polymerization initiated potassium 1-methoxy-2-propoxide/1-methoxy-2-propanol, in which in the presence of the same ligand M n increases to ~12 400 for the same ratio of reagents. The mechanism of studied processes was discussed.

Application of Dipotassium Glycoxides–Activated 18-Crown-6 for the Synthesis of Poly(propylene oxide) with Increased Molar Mass

Mono- and dipotassium salts of dipropylene glycol were applied for the polymerization of propylene oxide in mild conditions, i.e., tetrahydrofuran solution at ambient temperature. The structure of polymers was investigated by use of 13C NMR and MALDI-TOF techniques. The structure depends strongly on the kind of initiator and additives that are used such as coronand 18-crown-6 and dipropylene glycol. The lowest unsaturation, represented by allyloxy starting groups, has the polymer obtained by use of monopotassium salt without the ligand. The highest unsaturation degree is for the polymer synthesized in the presence of dipotassium salt–activated 18-crown-6. This polymer, obtained at high initial monomer concentration and low initial concentration of initiator, consists of two fractions, i.e., a low molar mass fraction (Mn = 9400) containing mainly macromolecules with alkoxide starting and end groups and a much higher molar mass fraction (Mn = 29500 g/mol) containing macromolecules with allyloxy starting groups and alkoxide or hydroxyl end groups. Addition of free glycol to this system decreases the molar mass of polymers. Similar results were obtained by use of dipotassium salts of other glycols. The mechanisms of the studied processes are discussed.

Characterization of Electrophoretically Deposited Chitosan Coatings on Ti13Zr13Nb Alloy for Biomedical Applications

The chitosan (CH) coatings on a Ti13Zr13Nb alloy substrate were obtained by electrophoretic deposition (EPD). The EPD yield was investigated under different deposition conditions. The microstructure of the CH coatings obtained by cataphoresis was studied by scanning electron microscopy and the chemical composition was examined using EDAX. The functional groups and formed phases were analyzed using Fourier transform infrared spectroscopy and X-ray diffraction, respectively. It was found that the CH coating thickness and porosity can be controlled by time and voltage used for the EPD process. It was ascertained that the studied EPD of the natural biopolymer, chitosan, in aqueous solution is applicable for the surface modification of the Ti13Zr13Nb implants to develop novel bioactive coatings.

Synthesis and spectral analysis of hyperbranched poly(ethers) containing carbazole or hydrazone groups

Hyperbranched poly(ethers) containing carbazole or hydrazone groups have been synthesized and investigated using absorption and luminescence spectroscopy. Purple-blue and greenish-blue fluorescence has been recorded for both polymer systems in tetrahydrofuran solution. Their spectral properties strongly depend on the monomer to initiator ratio and the kind of end groups.

Novel tumor protein markers collection by the use of highly porous organic material for the upper and lower respiratory system – preliminary results

In the era of XXI century, when modern imaging techniques allows to increase detection of upper and lower respiratory tract cancer, still almost 75% of patients are diagnosed at an advantage stage. A very important problem in diagnostic practice is a general trend to use routine methods and the lack of new techniques exploration. Nowadays laboratory diagnosticians known defects of used methods which result limited effectiveness. Despite this fact too little attention is paid to the confrontation of biomedical and physicochemical views what follows to develop new methods within the framework of interdisciplinary research.