Assessment of block and random copolymer overlayers on polymer optical fibers towards protein detection through electrostatic interaction

A simple fiber optic based scheme for the selective detection of proteins, based on surface electrostatic interactions, is presented. The implementation of this method is conducted by using a modified polymer optical fiber's (POF) surface and thin overlayers of properly designed sensitive copolymer materials with predesigned molecular characteristics. Block poly(styrene-b-2vinylpyridine) (PS-b-P2VP) and random poly(styrene-r-2vinylpyridine) (PS-r-P2VP) copolymers of the same monomers and similar molecular weights, were modified and used as sensing materials. This configuration proved to be efficient concerning the fast detection of charged proteins, and also the efficient discrimination of differently charged proteins such as lysozyme (LYS) and bovine serum albumin (BSA). Results on the sensing performance of block and random copolymers are also discussed drawing conclusion on their efficiency given their considerable different fabrication cost

Protein detection by polymer optical fibers sensitized with overlayers of block or random copolymers

In this study a low cost and low complexity optical detection method of proteins is presented by employing a detection scheme based on electrostatic interactions, and implemented by sensitization of a polymer optical fiber (POF) surface by thin overlayer of properly designed sensitive copolymer materials with predesigned charges. This method enables the fast detection of proteins having opposite charge to the overlayer, and also the effective discrimination of differently charged proteins like lysozyme (LYS) and bovine serum albumin (BSA). More specifically, as sensitive materials here was used the block and the random copolymers of the same monomers, namely the block copolymer poly(styrene-b-2vinylpyridine) (PS-b-P2VP) and the corresponding random polymer poly(styrene-r-2-vinylpyridine) (PS-r-P2VP), of similar composition and roughly similar molecular weight. Moreover, this work focused on the comparison of the aforementioned sensitive materials regarding the way in which they can adapt on sensing optical platforms and constitute functional sensing bio-materials

Lysozyme complexes with thermo- and pH-responsive PNIPAM-b-PAA block copolymer

Lysozyme is an enzyme responsible for the damage of bacterial cell walls and is abundant in a number of secretions such as tears and human milk. In the present study, we investigated the structure, the physicochemical characteristics, and the temperature-responsiveness of lysozyme complexes with poly(N-isopropylacrylamide)-b-poly(acrylic acid) block polyelectrolyte in aqueous media. A gamut of light-scattering techniques and fluorescence spectroscopy were used in order to examine the complexation process, as well as the structure, solution behavior, and temperature response of the nanosized complexes. The concentration of copolymer polyelectrolyte was kept constant. The values of the scattering intensity, I90, which is proportional to the mass of the species in solution, increased gradually as a function of CLYS, providing proof of the occurring complexation, while the size of the nanostructures decreased. The structure of the complexes became more open as the CLYS increased. The increase of the salinity did not affect the structural characteristics of the supramolecular nanoparticulate aggregates. On the other hand, the physicochemical and structural characteristics of the complexes changed upon increasing temperature, and the changes depended on the initial ratio block polyelectrolyte/lysozyme. The knowledge on developing block polyelectrolyte/protein complexes through electrostatic interactions, obtained from this investigation, may be applied to the design of nutraceuticals. © 2017, Springer Science+Business Media Dordrecht

The modulation of physicochemical characterization of innovative liposomal platforms: the role of the grafted thermoresponsive polymers

This study is focused on chimeric advanced drug delivery systems and specifically on thermosensitive liposomes, combining lipids and thermoresponsive polymers. In this investigation, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) chimeric liposomal systems were prepared, incorporating the homopolymer C12H25-poly(N-isopropylacrylamide)-COOH (C12H25-PNIPAM-COOH) and the block copolymer poly(n-butylacrylate-b-N-isoropylacrylamide) (PnBA-PNIPAM), at six different molar ratios. Both of these polymers contain the thermoresponsive PNIPAM block, which exhibits lower critical solution temperature (LCST) at 32 °C in aqueous solutions, changing its nature from hydrophilic to hydrophobic above LCST. During the preparation of liposomes, the dispersions were observed visually, while after the preparation we studied the alterations of the physicochemical characteristics, by measuring the size, size distribution and ζ-potential of prepared liposomes. The presence of polymer, either C12H25-PNIPAM-COOH or PnBA-PNIPAM, resulted in liposomes exhibiting different physicochemical characteristics in comparison to conventional DPPC liposomes. At the highest percentage of the polymeric guest, chimeric liposomes were found to retain their size during the stability studies. The incorporation of the appropriate amount of these novel thermoresponsive polymers yields liposomal stabilization and imparts thermoresponsiveness, due to the functional PNIPAM block. © 2015 Informa UK Limited, trading as Taylor & Francis Group

Calorimetric study on pH-responsive block copolymer grafted lipid bilayers: rational design and development of liposomes

This study is focused on chimeric advanced drug delivery nanosystems and specifically on pH-sensitive liposomes, combining lipids and pH-responsive amphiphilic block copolymers. Chimeric liposomes composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and two different forms of block copolymers, i.e. poly(n-butylacrylate)-b-poly(acrylic acid) (PnBA-b-PAA) at 70 and 85% content of PAA at six different molar ratios, each form respectively. PAA block exhibits pH-responsiveness, because of the regulative group of –COOH. –COOH is protonated under acidic pH (pKa ca. 4.2), while remains ionized under basic or neutral pH, leading to liposomes repulse and eventually stability. Lipid bilayers were prepared composed of DPPC and PnBA-b-PAA. Experiments were carried out using differential scanning calorimetry (DSC) in order to investigate their thermotropic properties. DSC indicated disappearance of pre-transition at all chimeric lipid bilayers and slight thermotropic changes of the main transition temperature. Chimeric liposomes have been prepared and their physicochemical characteristics have been explored by measuring the size, size distribution and ζ-potential, owned to the presence of pH-responsive polymer. At percentages containing medium to high amounts of the polymer, chimeric liposomes were found to retain their size during the stability studies. These results were well correlated with those indicated in the DSC measurements of lipid bilayers incorporating polymers in order to explain their physicochemical behavior. The incorporation of the appropriate amount of these novel pH-responsive block copolymers affects thus the cooperativity, the liposomal stabilization and imparts pH-responsiveness. © 2015 Taylor & Francis

Design and development of pH-sensitive liposomes by evaluating the thermotropic behavior of their chimeric bilayers

This study is focused on mixed/chimeric advanced drug delivery nanosystems and specifically on pH-sensitive liposomes, combining lipids and pH-responsive amphiphilic block copolymers. Chimeric liposomes are composed of hydrogenated soy phosphatidylcholine (HSPC) and two different poly(n-butylacrylate)-b-poly(acrylic acid) (PnBA-b-PAA) block copolymers with 85 and 70% content of PAA, at six different molar ratios. PAA block exhibits pH responsiveness, because of the regulative group of –COOH. Chimeric bilayers are composed of HSPC and PnBA-b-PAA. Experiments are carried out by using differential scanning calorimetry (DSC) in order to investigate their thermotropic properties. DSC indicated disappearance of the pretransition effect in all chimeric lipid bilayers, at both buffers [phosphate buffer saline (PBS) and citrate buffer], and slight changes of the main transition temperature (Tm). Contrariwise, the cooperativity (T1/2) presented alterations between the two different buffers. Chimeric liposomes have been prepared and their physicochemical characteristics have been explored in PBS and citrate buffer by measuring the size, size distribution and ζ-potential. Liposomes are found to retain the mean value of their size during the stability studies. The physicochemical characteristics and the stability assessment of chimeric liposomes are correlated with DSC measurements of mixed bilayers. The incorporation of the appropriate amount of these novel pH-responsive block copolymers affects the cooperativity and the liposomal stabilization and imparts pH responsiveness (functionality), which was confirmed by performing experiments in acidic environment (citrate buffer). In conclusion, the results from DSC measurements provide useful information regarding the quality by design process for rationally preparing mixed/chimeric liposomal platforms to incorporate bioactive molecules. © 2017, Akadémiai Kiadó, Budapest, Hungary

Design and development of pH-responsive HSPC:C12H25-PAA chimeric liposomes

The application of stimuli-responsive medical practices has emerged, in which pH-sensitive liposomes figure prominently. This study investigates the impact of the incorporation of different amounts of pH-sensitive polymer, C12H25-PAA (poly(acrylic acid) with a hydrophobic end group) in l-α-phosphatidylcholine, hydrogenated (Soy) (HSPC) phospholipidic bilayers, with respect to biomimicry and functionality. PAA is a poly(carboxylic acid) molecule, classified as a pH-sensitive polymer, whose pH-sensitivity is attributed to its regulative –COOH groups, which are protonated under acidic pH (pKa ∼4.2). Our concern was to fully characterize, in a biophysical and thermodynamical manner, the mixed nanoassemblies arising from the combination of the two biomaterials. At first, we quantified the physicochemical characteristics and physical stability of the prepared chimeric nanosystems. Then, we studied their thermotropic behavior, through measurement of thermodynamical parameters, using Differential Scanning Calorimetry (DSC). Finally, the loading and release of indomethacin (IND) were evaluated, as well as the physicochemical properties and stability of the nanocarriers incorporating it. As expected, thermodynamical findings are in line with physicochemical results and also explain the loading and release profiles of IND. The novelty of this investigation is the utilization of these pH-sensitive chimeric advanced Drug Delivery nano Systems (aDDnSs) in targeted drug delivery which relies entirely on the biophysics and thermodynamics between such designs and the physiological membranes and environment of living organisms. © 2016 Informa UK Limited, trading as Taylor & Francis Group

A dual-stimuli-responsive polymer into phospholipid membranes: A thermotropic approach

In this study, we investigate the thermotropic effects of diblock copolymer poly(N-isopropylacrylamide)-block-poly(acrylic acid) (PNIPAM-b-PAA) on fully hydrated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayers and its ability to alter the membranes' organization, fluidity and phase behavior. The composition of the diblock copolymer and the nature of dispersion medium (pH and ionic strength) were also examined. For these purposes, pure DPPC lipid and polymer-lipid mixed systems, hydrated in three different dispersion media (i.e., HPLC-grade water, phosphate buffer saline and hydrochloric acid solution of pH 4.5), were investigated by differential scanning calorimetry. Two compositions of PNIPAM-b-PAA with different molar ratio of the polymeric blocks were used. PNIPAM-b-PAA presents great scientific interest due to the combination of the special characteristics of its homopolymer components; it is dual responsive both in temperature and in pH changes. The incorporation of the PNIPAM-b-PAA into the DPPC bilayers causes particularly significant perturbations in their thermotropic behavior, slightly different in each dispersion medium. The results indicated the ordering of the polymer guest near the polar head group surface probably by its PAA block and, on the other hand, the penetration of the PNIPAM block into the hydrophobic bilayer core, causing membrane disruption in a temperature-depended manner. We can conclude that the lipid-polymer interactions seem to be affected by the pH and the ionic strength of the hydration medium, as well as the polymer content incorporated in the DPPC bilayer. These studies could be a roadmap in order to rationally design and develop chimeric liposomes. © 2015 Akadémiai Kiadó, Budapest, Hungary