Polymers, Volume 7, Issue 12 (December 2015) – 16 articles

Porous materials, especially microparticles (MP), are utilized in almost every field of engineering and science, ranging from healthcare materials (drug delivery to tissue engineering) to environmental engineering (biosensing to catalysis). Here, we utilize the single needle electrospraying technique (as opposed to complex systems currently in development) to prepare a variety of poly(ε-caprolactone) (PCL) MPs with diverse surface morphologies (variation in pore size from 220 nm to 1.35 µm) and architectural features (e.g., ellipsoidal, surface lamellar, Janus lotus seedpods and spherical). This is achieved by using an unconventional approach (exploiting physicochemical properties of a series of non-solvents as the collection media) via a single step. Sub-micron pores presented on MPs were visualized by electron microscopy (demonstrating a mean MP size range of 7–20 μm). The present approach enables modulation in morphology and size requirements for specific applications (e.g., pulmonary delivery, biological scaffolds, multi-stage drug delivery and biomaterial topography enhancement). Differences in static water contact angles were observed between smooth and porous MP-coated surfaces. This reflects the hydrophilic/hydrophobic properties of these materials. Full article

N-substituted chitosan derivatives were synthesized through condensation with a number of selected aryl and heteroaryl aldehydes. The synthesis of the amino-derivatives has been carried out by reductive amination with sodium borohydride as reducing agent. Their structures were characterized by (FT-IR, ¹HNMR, and XRD). The antimicrobial activity of Chitosan Schiff’s base (CSB) derivatives were investigated against four types of bacteria and two crop-threatening pathogenic fungi, and the results indicated that the antibacterial and antifungal activities of the investigated derivatives are very promising. Additionally, different concentrations of the triazolo-Schiff’s base derivative 3c were used for cytotoxicity screening against Human Breast Adenocarcinoma Cells (MCF-7), Human Colon Carcinoma Cells (HCT-116), and Human Hepatocellular Liver Carcinoma Cells (HepG-2), and the obtained data revealed that the examined compounds have an excellent cell growth inhibitory effects on the cell lines as compared to standard. Full article

The stabilization and reinforcement of damaged barrel vaults with lunettes over an arcaded walk, applying composite strips based on high-strength carbon fibers and epoxy resin, was performed during the restoration of a historic monastery. The application of reinforcing composite strips in the soffit of damaged barrel vaults was preceded by relatively extensive experimental research and theoretical analyses. This method significantly reduces the interventions into and the degradation of the original historic structure (surface application) and is reversible. Full article

Biological tissues are viscoelastic, demonstrating a mixture of fluid and solid responses to mechanical strain. Whilst viscoelasticity is critical for native tissue function, it is rarely used as a design criterion in biomaterials science or tissue engineering. We propose that viscoelasticity may be tailored to specific levels through manipulation of the hydrogel type, or more specifically the proportion of physical and chemical crosslinks present in a construct. This theory was assessed by comparing the mechanical properties of various hydrogel blends, comprising elastic, equilibrium, storage and loss moduli, as well as the loss tangent. These properties were also assessed in human articular cartilage explants. It was found that whilst very low in elastic modulus, the physical crosslinks found in gellan gum-only provided the closest approximation of loss tangent levels found in cartilage. Blends of physical and chemical crosslinks (gelatin methacrylamide (GelMA) combined with gellan gum) gave highest values for elastic response. However, a greater proportion of gellan gum to GelMA than investigated may be required to achieve native cartilage viscoelasticity in this case. Human articular chondrocytes encapsulated in hydrogels remained viable over one week of culture. Overall, it was shown that viscoelasticity may be tailored similarly to other mechanical properties and may prove a new criterion to be included in the design of biomaterial structures for tissue engineering. Full article

The article focuses on investigation of the effects of usage of acidic electrolyzed water (AEW) with different sodium chloride concentration (0.001%, 0.01%, and 0.1%) for the preparation of carrageenan and gelatine hydrosols and hydrogels. To determine physiochemical properties of hydrosols, the pH, oxidation-reduction potential (ORP), available chloride concentration (ACC) and rheological parameters such us gelation and flow temperatures were measured. The samples were also characterized using Fourier transform infrared spectroscopy (FT IR) and texture profile analysis (TPA). Additionally, the article contains an analysis of antibacterial activity of carrageenan and gelatine hydrosols incorporated with acidic electrolyzed water, against Staphylococcus aureus and Escherichia coli. The FT IR spectra demonstrated that the structure of gelatine and carrageenan are not significantly affected by electrolyzed NaCl solution components. Furthermore, TPA analysis showed that the use of AEW did not cause undesirable changes in hydrogels layer. The microbiological analysis confirmed inhibition of bacterial growth by hydrosols to about 2.10 log reduction. The results showed that the range of reduction of microorganisms depends on the type AEW used. This might be explained by the fact that the lowest pH and the highest ACC values of hydrosols were obtained for samples with the longest period of exposure to electrolysis (10 min) and the highest amount of NaCl (0.1% w/v). These results suggest that hydrogels and hydrosols incorporated with AEW may be used for food preservation. Full article

A new water-soluble pyrene-containing fluorescent polymer, 1-{3′-S-[poly(acryloyl ethylene diamine hydrochloride)-2′-methyl propionic acid]}propionyloxy hexyloxy pyrene (P3) with defined structure, was designed and synthesized using the click reaction between thiol and a carbon-carbon double bond. The intermediate products P1 (S-1-dodecyl-S′-[poly(N-Boc-acryloyl ethylene diamine)-2′-methyl propionic acid]trithiocarbonate) and AHP (1-(acryloyloxy hexyloxy)pyrene) were prepared via reversible addition fragmentation chain transfer (RAFT) polymerization and Williamson synthesis, respectively. Conjugating AHP with P1, P2 (1-{3′-S-[poly(N-butoxycarbonyl-acryloyl ethylene diamine)-2″-methyl propionic acid]} propionyloxy hexyloxy pyrene) was synthesized, adopting both the reduction reaction of a trithioester bond of P1 to thiol and the click reaction between thiol and the carbon-carbon double bond of AHP simultaneously. P3 was obtained by the deprotection of the resulting Boc-protected polymer (P2) with aqueous HCl. The experiment results showed that P2 exhibited a bright blue-violet emission band at approximately 387–429 nm. After deprotection, P3 displayed good solubility in water and not only exhibited a blue-violet fluorescence emission band at approximately 387–429 nm in aqueous solution but also had the similar photoluminescent spectra to those of AHP and P2 in dichloromethane. The fluorescence quantum yields of P2 in dilute tetrahydrofuran and P3 in a dilute aqueous solution were 0.44 and 0.39, respectively. This experiment provided a novel insight into the study of water-soluble fluorescent polymers. Full article

The reactivity of the bimetallic complex (Ph₄P)₂[W₂(μ-Br)₃Br₆] ({W ^2.5 W}⁷⁺, a′²e³) towards ring opening metathesis polymerization (ROMP) of norbornene (NBE) and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA), is presented. Our results show that addition of a silver salt (AgBF₄) is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF) producing polyphenylacetylene (PPA) in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH₂Cl₂, providing high yields of polymers. ¹³C Cross Polarization Magic Angle Spinning (CPMAS) spectra of insoluble polynorbornadiene (PNBD) and polydicyclopentadiene (PDCPD) revealed the operation of two mechanisms (metathetic and radical) for cross-linking, with the metathesis pathway prevailing. Full article

This paper presents the experimental results of steel plates strengthened with carbon fiber reinforced polymer (CFRP) sheets under tensile load. The number of CFRP layers (ranging from one to four), strengthening schemes (single-sided and double-sided bonding), and temperatures (ranging from 25 to 120 °C) were investigated. Results showed that the number of CFRP layers and strengthening schemes had insignificant effects on failure modes of specimens. The failure modes were dominated by the degradation of resin matrix at temperatures lower than T_g + 10 or 20 °C, where T_g is the glass transition temperature, and were dominated by the volume decrease of resin matrix at temperatures above that. Through bonding CFRP sheets, the ultimate load and post-elastic stiffness of specimens were significantly increased. However, the increase in the number of CFRP layers also led to the decrease in strengthening and stiffening efficiency. The double-sided strengthened specimens showed more preferable mechanical properties than the single-sided strengthened specimens. As temperature increased, significant decreases in ultimate load and post-elastic stiffness were observed. Analytical modeling to predict the mechanical properties at ambient and elevated temperatures were conducted, respectively. The modeling results were verified by the test data. Full article

In this study, free-standing expanded graphite chitosan (EG-chitosan) nanocomposite films have been prepared using a novel green and simple preparation method, starting from a commercial expandable graphite (GIC). The in situ exfoliation of GIC by a solvent-free sonication method was monitored as a function of the process parameters using X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic light scattering (DLS) and UV-visible transmittance (UV-VIS) analyses. The optimal process parameters were selected in order to obtain an efficient dispersion of EG in chitosan solutions. The effective EG amount after the in situ exfoliation was also determined by thermogravimetric analyses. Full article

A comparative study of thermal response of poly(vinyl methyl ether) in the presence of different hydrophilic and hydrophobic additives was performed by Nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and optical microscopy. The effect of polymer concentration and additive content on the appearance and extent of the phase transition was determined. A detailed study of interaction mechanism in solutions with two hydrophobic additives showed differences in the way in which polymer globules are formed. For solutions containing t-butyl methyl ketone and t-butanol, measurements of ¹H spin-spin relaxations showed the presence of water and additive molecules bound in PVME globular structures. These originally-bound molecules are then slowly released from the globular-like structures. Incorporation of molecules into the globules disrupts the cooperativity of the transition and affects the size of globular structures. Full article

The ABA tri-block copolymer poly(2-methyloxazoline)–poly(dimethylsiloxane)–poly(2-methyloxazoline) (PMOXA–PDMS–PMOXA) is known for its capacity to mimic a bilayer membrane in that it is able to form vesicular polymersome structures. For this reason, it is the subject of extensive research and enables the development of more robust, adaptable and biocompatible alternatives to natural liposomes for biomedical applications. However, the poor solubility of this polymer renders published methods for forming vesicles unreproducible, hindering research and development of these polymersomes. Here we present an adapted, simpler method for the production of PMOXA–PDMS–PMOXA polymersomes of a narrow polydispersity (45 ± 5.8 nm), via slow addition of aqueous solution to a new solvent/polymer mixture. We then magnetically functionalise these polymersomes to form magnetopolymersomes via in situ precipitation of iron-oxide magnetic nanoparticles (MNPs) within the PMOXA–PDMS–PMOXA polymersome core and membrane. This is achieved using electroporation to open pores within the membrane and to activate the formation of MNPs. The thick PMOXA–PDMS–PMOXA membrane is well known to be relatively non-permeable when compared to more commonly used di-block polymer membranes due a distinct difference in both size and chemistry and therefore very difficult to penetrate using standard biological methods. This paper presents for the first time the application of electroporation to an ABA tri-block polymersome membrane (PMOXA–PDMS–PMOXA) for intravesicular in situ precipitation of uniform MNPs (2.6 ± 0.5 nm). The electroporation process facilitates the transport of MNP reactants across the membrane yielding in situ precipitation of MNPs. Further to differences in length and chemistry, a tri-block polymersome membrane structure differs from a natural lipid or di-block polymer membrane and as such the application and effects of electroporation on this type of polymersome is entirely novel. A mechanism is hypothesised to explain the final structure and composition of these biomedically applicable tri-block magnetopolymersomes. Full article

Many existing reinforced concrete structures were constructed with substandard characteristics. Low quality concrete, poor transverse reinforcement details and insufficient flexural strength are among the most common deficiencies. While substandard structures are in need of retrofitting, particularly in seismic areas, problems such as high costs and disturbance to occupants are major obstacles for retrofit interventions. Fiber reinforced polymers can provide feasible retrofit solutions with minimum disturbance to occupants. In this study, the basic aim is to investigate the flexural seismic performance of substandard reinforced concrete columns retrofitted with embedded longitudinal fiber reinforced polymer reinforcement without increasing the original dimensions of the columns. In the experimental study, the reference and retrofitted columns were tested under constant vertical and reversed cyclic lateral loads. Three different connection methods of aramid fiber reinforced polymer reinforcement to the footing were investigated experimentally. A significant enhancement was obtained in lateral flexural strength through the proposed retrofitting method. Furthermore, it was observed that the cyclic lateral drift capacities of the retrofitted columns were as high as 3%, which can be deemed as quite satisfactory against seismic actions. The comparison of the experimental data with analytical calculations revealed that a conventional design approach assuming composite action between concrete and fiber reinforced polymer reinforcement can be used for flexural retrofit design. Experimental results also demonstrated that strain limit for longitudinal fiber reinforced polymer (FRP) reinforcement should be remarkably lower in case of reversed cyclic loading conditions. Full article

Two ethylene-octene copolymers (EOC) with the same melt flow index (MFI = 3 g/10 min) but different octene contents, being 20 and 35 wt % (EOC-20 and EOC-35), were compared with regard to sensitivity to electron beam crosslinking. Dynamic mechanical analysis (DMA) revealed a large influence of the octene content on the storage modulus and the glass transition temperature (T_g) but a smaller influence of irradiation on the properties below melting point (T_m). Rheology at 150 °C pointed out large differences in samples crosslinked in the 0–60 kGy range and at lower frequencies (0.1–1 Hz). The loss factor tanδ confirmed that before irradiation the two copolymers were very similar, while after irradiation to 120 kGy, the EOC-35 had considerably lower tanδ than EOC-20, which corresponds to a better elasticity (or a higher level of crosslinking). A high-temperature creep test showed a considerably lower creep for EOC with a higher octene content. An analysis of the insoluble gel content exhibited higher values for EOC-35 confirming a higher level of crosslinking. Analysis according to the Charlesby-Pinner equation revealed increased crosslinking-to-scission ratio, G(X)/G(S), for EOC-35. While the G(X) value changed only slightly, a significant decrease in the G(S) value was discovered. Full article

The production of silica is performed by mixing an inorganic, silicate-based precursor and an acid. Monomeric silicic acid forms and polymerizes to amorphous silica particles. Both further polymerization and agglomeration of the particles lead to a gel network. Since polymerization continues after gelation, the gel network consolidates. This rather slow process is known as “natural syneresis” and strongly influences the product properties (e.g., agglomerate size, porosity or internal surface). “Enforced syneresis” is the superposition of natural syneresis with a mechanical, external force. Enforced syneresis may be used either for analytical or preparative purposes. Hereby, two open key aspects are of particular interest. On the one hand, the question arises whether natural and enforced syneresis are analogous processes with respect to their dependence on the process parameters: pH, temperature and sample size. On the other hand, a method is desirable that allows for correlating natural and enforced syneresis behavior. We can show that the pH-, temperature- and sample size-dependency of natural and enforced syneresis are indeed analogous. It is possible to predict natural syneresis using a correlative model. We found that our model predicts maximum volume shrinkages between 19% and 30% in comparison to measured values of 20% for natural syneresis. Full article

Pultrusion is an easy molding method of fiber-reinforced polymer (FRP) to obtain a long composite material with a uniform cross-section at relatively low cost. In some cases, pultruded FRPs are now used in bridges and deck projects. Since the application of pultruded FRP as a structural material is increasing, a study on the durability of pultruded FRP under outdoor conditions is necessary in terms of safety. Some studies have shown that pultruded glass fiber-reinforced polymer (GFRP) exhibits a slight reduction in mechanical properties during outdoor exposure. Since pultruded GFRP consists of multi-layers, the change of mechanical properties in each layer is important to understand. In this study, an outdoor exposure test on pultruded GFRP for 10 years was conducted with three types of pultruded GFRP, which have different laminate systems, including surface-coated specimens of each type. Changes of strength and elastic modulus due to outdoor exposure were discussed with a focus on the contribution of each layer based on the rule of mixtures. Full article

We present the synthesis and characterization of well-defined polycationic copolymers containing thiazole dyes in the side chain. Atom transfer radical polymerization (ATRP) was used for the copolymerization of 3-azidopropyl methacrylate (AzPMA) and N,N-dimethylaminoethyl methacrylate (DMAEMA) of different composition. Thiazole-based alkyne-functionalized dyes (e.g., 5-methyl-4-(prop-2-yn-1-yloxy)-2-(pyridin-2-yl)thiazole, (MPPT)) were afterwards covalently attached using copper catalyzed azide alkyne cycloadditions (CuAAC) reaching contents of up to 9 mol % dye. Subsequent quaternization of the tertiary nitrogen of DMAEMA with strong methylation agents (e.g., methyl iodide) led to permanently charged polyelectrolytes. The materials were characterized by size exclusion chromatography, as well as NMR- and UV/VIS-spectroscopy. Particular attention is paid to the spectroscopic properties of the dyes in the side chain upon environmental changes such as pH and salinity. We anticipate the application of such precisely functionalized polyelectrolytes as temperature- and pH-responsive sensors in biomedical applications, e.g., within interpolyelectrolyte complexes. Concerning the latter, first complex formation results are demonstrated. Full article