Block Copolymer Nanosystems Encapsulating Magnetic Nanoparticles and Drug.

The goal of this study was to investigate the solution behavior of nanosystems composed of self-assembling amphiphilic diblock copolymers, poly(ethylene oxide-b-phenyl oxazoline) and poly(isoprene-b-ethylene oxide) (PEO-b-PPhOx and PI-b-PEO), with encapsulated iron oxide nanoparticles (γ-Fe2O3). The hybrid nanosystems were tested in aqueous solution, under physiological conditions and in mixtures with serum proteins. Light scattering methods were used to probe changes in size and mass of the formed aggregates in different solution conditions and as a function of storage time. The developed stable hybrid systems with encapsulated magnetic nanoparticles were able to entrap the anti-inflammatory drug, indomethacin. This work demonstrates versatile nanosystems with metal oxide characteristics for bio-imaging and the potential for drug delivery in aqueous media.

Kinetics of Light-Induced Concentration Patterns in Transparent Polymer Solutions.

When exposed to weak visible laser light, solutions of common polymers like poly(isoprene) and poly(butadiene) respond by local concentration variations, which in turn lead to refractive index changes. Various micropatterns have been recently reported, depending mostly on the solvent environment and the irradiation conditions. Here, we focused on the simpler case of single polymer-rich filaments and we employed phase contrast microscopy to systematically investigate the influence of laser illumination and material parameters on the kinetics of the optically induced local concentration increase in the polydiene solutions. The refractive index contrast of the formed filaments increased exponentially with the laser illumination time. The growth rate exhibited linear dependence on the laser power and increased with polymer chain length in semidilute solutions in good solvents. On the contrary, the kinetics of the formed filaments appeared to be rather insensitive to the polymer concentration. Albeit the origin of the peculiar light field-polymer concentration coupling remains yet elusive, the new phenomenology is considered necessary for the elucidation of its mechanism.

Carbon quantum dots/block copolymer ensembles for metal-ion sensing and bioimaging.

Fluorescent carbon quantum dots (CQDs) rich in amine moieties that can be easily protonated under acidic conditions were electrostatically interacted with diblock copolymer poly[sodium(carboxylate sulfamate) isoprene]-b-poly(ethylene oxide) (CSS-IEO-3) possessing negatively charged sulfamate and carboxylate species on the CSS part of the diblock copolymer. The so-formed CQDs/CSS-IEO-3 material was found to be stable in a neutral and high salinity environment, which is critical when aiming for biological applications. Moreover, the photoluminescence of CQDs within CQDs/CSS-IEO-3, with emission at 420 nm upon excitation at 320 nm, was unaffected by pH and salinity changes, denoting the absence of significant aggregation phenomena and highlighting the potential of CQDs/CSS-IEO-3 for bioimaging. The photoluminescence of CQDs/CSS-IEO-3 was employed to develop a selective and sensitive method for the facile detection of Fe3+, in the presence of other metal salts, with a detection limit of 8.37 µM. Furthermore, integration of bovine serum albumin (BSA) furnished the three-component CQDs/CSS-IEO-3·BSA nanoensemble, without causing cytotoxicity when subjected to RKO human colon adenocarcinoma cell line. Evidently, confocal fluorescence microscopy allowed the imaging of CQDs/CSS-IEO-3·BSA within living cells, and illustrated its application potential for bioimaging and drug delivery.

Single-Step Functionalization and Exfoliation of Graphene with Polymers under Mild Conditions.

The simultaneous polymer functionalization and exfoliation of graphene sheets by using mild bath sonication and heat treatment at low temperature is described. In particular, free-radical polymerization of three different vinyl monomers takes place in the presence of graphite flakes. The polymerization procedure leads to the exfoliation of graphene sheets and at the same time the growing polymer chains are attached onto the graphene lattice, which gives solubility and stability to the final graphene-based hybrid material. The polymer-functionalized graphene sheets possess fewer defects as compared with previously reported polymer-functionalized graphene. The success of the covalent functionalization and exfoliation of graphene was confirmed by using a variety of complementary spectroscopic, thermal, and microscopy techniques, including Raman, IR and UV/Vis spectroscopy, thermogravimetric analysis, and transmission electron microscopy.

Photocatalytic applications with CdS • block copolymer/exfoliated graphene nanoensembles: hydrogen generation and degradation of Rhodamine B.

Amphiphilic block copolymer poly(isoprene-b-acrylic acid) (PI-b-PAA) was used to stabilize exfoliated graphene in water, allowing the immobilization of semiconductor CdS nanoparticles forming CdS â€¢ PI-b-PAA/graphene. Characterization using high-resolution transmission electron microscopy and energy-dispersive x-ray spectroscopy proved the success of the preparation method and revealed the presence of spherical CdS. Moreover, UV-Vis and photoluminescence assays suggested that electronic interactions within CdS â€¢ PI-b-PAA/graphene exist as evidenced by the significant quenching of the characteristic emission of CdS by exfoliated graphene. Photoillumination of CdS â€¢ PI-b-PAA/graphene, in the presence of ammonium formate as a quencher for the photogenerated holes, resulted in the generation of hydrogen by water splitting, monitored by the reduction of 4-nitroaniline to benzene-1,4-diamine (>80 ± 4% at 20 min; 100% at 24 min), much faster and more efficient compared to when reference CdS â€¢ PI-b-PAA was used as the photocatalyst (<30 ± 3% at 20 min; 100% at 240 min). Moreover, Rhodamine B was photocatalytically degraded by CdS â€¢ PI-b-PAA/graphene, with fast kinetics under visible light illumination in the presence of air. The enhancement of both photocatalytic processes by CdS â€¢ PI-b-PAA/graphene was rationalized in terms of effective separation of holes and electrons, contrary to reference CdS â€¢ PI-b-PAA, in which rapid recombination of the hole-electron pair is inevitable due to the absence of exfoliated graphene as a suitable electron acceptor.

Τhe effect of silica nanoparticles on the thermomechanical properties and degradation behavior of polylactic acid.

In this work a series of polylactic acid/SiO2 nanocomposites have been prepared by a melt mixing procedure. The dispersion quality was examined by scanning electron microscopy. To study the degradation behavior of the polylactic acid/nanocomposites prepared, the samples were immersed in a buffer solution at a temperature of 37℃ with a pH of 7.4 for a time period of up to 23 weeks. These conditions simulate those in the human body, appropriate in medical applications. In order to assess their suitability in biomedical applications, we investigated the biocompatibility of these materials in terms of cell viability, growth, and morphology. A good initial cell adhesion has been detected, supporting their potential use in bone tissue engineering applications. The hydrolytic degradation of polylactic acid, under the prescribed conditions, was studied by the molecular weight reduction in terms of size exclusion chromatography, whereas the progress of thermal stability of polylactic acid and polylactic acid/nanocomposites during aging was tested by thermogravimetric analysis. The evolution of the materials' thermomechanical properties during aging was studied by differential scanning calorimetry, dynamic mechanical analysis, and tensile testing. The crystallization behavior in polylactic acid and the way it is affected by the presence of nanofillers during degradation procedure has been studied and values of 44% crystallinity increment have been found. At the specific aging conditions studied, silica nanoparticles accelerate the degradability of polylactic acid, having a higher impact on Young's modulus, under the specified aging conditions, for 7 weeks and hereafter this acceleration is retarded, due to the crystallinity increment, as a result of the molecular weight reduction.

Enhanced gene expression promoted by hybrid magnetic/cationic block copolymer micelles.

We report on novel gene delivery vector systems based on hybrid polymer-magnetic micelles. The hybrid micelles were prepared by codissolution of hydrophobically surface modified iron oxide and amphiphilic polystyrene-b-poly(quaternized 2-vinylpyridine) block copolymer (PS-b-P2QVP) in organic solvent. After extensive dialysis against water, micelles with positively charged hydrophilic corona of PQVP and hydrophobic PS core were prepared, in which magnetic nanoparticles were randomly distributed. The hybrid micelles were used to form complexes with linear (salmon sperm, 2000 bp, corresponding to M(w) of 1.32 × 10(6) Da) and plasmid (pEGFP-N1, 4730 bp, corresponding to M(w) of 3.12 × 10(6) Da) DNA. The resulting magnetopolyplexes of phosphate:amine (P/N) ratios in the 0.05-20 range were characterized by light scattering, ζ-potential measurements, and transmission electron microscopy as well as cytotoxicity and gel retardation assays. The investigated systems displayed a narrow size distribution, particle dimensions below 360 nm, whereas their ζ-potential values varied from positive to negative depending of the P/N ratio. The resulting vector nanosystems exhibited low toxicity. They were able to introduce pEGFP-N1 molecules into the cells. The application of a magnetic field markedly boosted the transgene expression efficiency of the magnetopolyplexes, which was even superior to those of commercial transfectants such as Lipofectamine and dendritic polyethylenimine.

Block copolymers for drug delivery nano systems (DDnSs).

The application of polymers in medicine, as components of drug carriers, as well as their synthetic strategies are considered essential for producing and developing new drug formulations against human deceases. The synthesis of block copolymers is a timeconsuming process with a high cost of the final product, although several block copolymer systems have been already commercialized successfully. The biocompatibility, the biodegradability and the non toxic profile of newly synthesized polymers towards healthy tissues, should be taken into account in order to be acceptable for biomedical applications. In this review article, focus is placed on new approaches and synthetic strategies for preparing novel block copolymers and their utilization as parts of new and advanced Drug Delivery nanoSystems (aDDnSs) with a Modulatory Controlled Release profile (MCR). Such complex and advanced nanosystems can alter the pharmacokinetic properties of the encapsulated drug and consequently its effectiveness. Emphasis is given to the use of living polymerization methodologies and post polymerization chemical transformation reactions for the synthesis of mainly diblock copolymers for novel drug delivery nanosystems. Issues related to self-assembly of block copolymers in solution toward formation of colloidal functional nanostructures that can serve as nanocontainers and nanocarriers, and strategies for controlling encapsulation of specific drugs are also discussed. Specific examples are reported mainly on diblock copolymer systems, including authors' recent work.

Synthesis and magnetic properties of Fe3O4 nanoparticles coated with biocompatible double hydrophilic block copolymer.

Fe3O4 nanoparticles coated with double hydrophilic biocompatible poly(sodium(2-sulfamate-3-carboxylate)isoprene)-b-poly(ethylene oxide) block copolymer were prepared by a one step precipitation method. The magnetic nanoparticles have 15 nm mean diameter (TEM), 68 nm hydrodynamic diameter, -30.10 mV zeta-potential and form very stable dispersion in aqueous media. Structural characterization using powder XRD and Mössbauer spectroscopy establish the magnetite phase, while thermogravimetric analysis and FT-IR spectroscopy confirm the presence of the block copolymer on the nanoparticles surface. The magnetic properties were determined using a vibrating sample magnetometer (VSM) at room temperature and reveal superparamagnetic behavior while the composite materials shows high saturation magnetization up to 67.7 emu/gr.

Dynamics at the air-water interface revealed by evanescent wave light scattering.

A new tool to study surface phenomena by evanescent wave light scattering is employed for an investigation of an aqueous surface through the water phase. When the angle of incidence passes the critical angle of total internal reflection, a high and narrow scattering peak is observed. It is discussed as an enhancement of scattering at critical angle illumination. Peak width and height are affected by the interfacial profile and the focusing of the beam. In addition, the propagation of capillary waves was studied at the surface of pure water and in the presence of latex particles and amphiphilic diblock copolymers. The range of the scattering vectors where propagating surface waves were detected is by far wider than standard surface quasi-elastic light scattering (SQELS) and comparable with those of X-ray photon correlation spectroscopy (XPCS).

Complexes between high charge density cationic polyelectrolytes and anionic single- and double-tail surfactants.

Polyelectrolyte/surfactant complexes formed between well-defined linear flexible polyelectrolytes, namely, quaternized poly[3,5-bis(dimethylaminomethylene)hydroxystyrene] (Q-N-PHOS), bearing two cationic sites on each repeating unit, and two different anionic surfactants, namely, sodium dodecyl sulfate (SDS) with one hydrocarbon tail and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with two hydrocarbon chains, are studied by means of fluorescence spectroscopy, electrophoretic, dynamic and static light scattering, and atomic force microscopy. Depending on the surfactant state in initial solutions (i.e., below or above nominal critical micelle concentration, cmc) and final (-/+) charge ratio, self-assembly in nanoparticles of variable size, stability, and effective charge is possible. Spherical, rather polydispserse complexes are formed in all cases. Critical aggregation concentrations (cac) depend on the surfactant type, while hydrophobicity of the main polyelectrolyte chain plays a role in colloidal stability of the complex nanoparticles.

Self-assembly in mixed aqueous solutions of amphiphilic block copolymers and vesicle-forming surfactant.

The self-assembly behavior of mixed solutions consisting of poly(isoprene-b-ethylene oxide) (IEO) copolymer micelles and vesicle-forming didodecyldimethylammonium bromide (DDAB) was investigated. Dynamic light scattering indicated the presence of two populations of nanoassemblies in the solutions. By aid of atomic force microscopy, the larger ones were identified as block copolymer modified surfactant vesicles (BCMSVs) and the smaller ones as surfactant-modified block copolymer micelles (SMBCMs). This identification is based on the amphiphilic character of the low and high molecular weight molecules and the notion that exchange of unimers of both types can take place between the initial nanoassemblies in aqueous solution. Electrophoretic light scattering experiments showed that the nanostructures carry positive charges originating from the surfactant. The sizes of the nanoassemblies depend on the relative concentrations of both components. The behavior of the mixed systems was also found to depend on block copolymer composition and temperature. Nanoassemblies of smaller sizes were formed at higher temperatures. BCMSVs and SMBCMs are thermosensitive, in contrast to the temperature stability of pure block copolymer micelles. On the other hand, BCMSVs showed lesser sensitivity to temperature increase compared to the pure DDAB vesicles. This indicates that incorporation of macromolecules into the DDAB bilayer increases the stability of the vesicles.

Aqueous dispersions of C60 fullerene by use of amphiphilic block copolymers: preparation and nonlinear optical properties.

The dispersion of the otherwise insoluble C60 fullerene in water is discussed. Amphiphilic block copolymers, namely, polystyrene-b-polyethylene oxide (PS-PEO), were found to be able to disperse C60 in aqueous solutions, where the polymer forms micelles with a hydrophobic PS core. The preparation protocol of the final solutions was found to play a crucial role in the ability of the block copolymer to disperse the C60 molecules. The C60 containing aggregates were studied using optical spectroscopy, light scattering, and scanning electron microscopy. In addition, their optical limiting action and nonlinear optical properties under visible nanosecond laser excitation were studied and compared with that of C60-toluene solutions.

Micelles of poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) terpolymers in aqueous media and their interaction with surfactants.

Well-defined poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) (PI-P2VP-PEO) triblock terpolymers were synthesized by anionic polymerization high-vacuum techniques. The terpolymers formed spherical three-layer (onion-type) micelles in neutral and acidic pH aqueous media as evidenced by static and dynamic light scattering. In pure water, kinetically frozen micelles with a core composed of a soft PI inner part and a hard P2VP outer shell and protected by a neutral PEO corona were formed. In acidic media the core was formed by the soft PI hydrophobic segment, whereas the corona consisted of an inner cationic polyelectrolyte P2VPH+ part and an outer PEO shell. The aggregation numbers were found to be high in all cases, due to the high hydrophobicity of the core-forming blocks. In the latter case an increase in size was observed due to the electrostatic repulsions between the P2VPH+ chains in the inner part of the corona, which is also responsible for the lower aggregation numbers observed in the acidic solutions. The interaction of these onion-type micelles with cationic (DTMAB) and anionic (SDS) surfactants led to the formation of mixed polymer/surfactant aggregates. Their structural characteristics could be varied by combining changes in surfactant type and concentration, solution pH and type of electrostatic interaction, leading to interesting, block-copolymer-based, environmentally responsive colloidal systems.

Pattern formation in homogeneous polymer solutions induced by a continuous-wave visible laser.

We report an unexpected nonphotothermal material organization induced by continuous-wave visible laser light at low power levels. This effect is observed along the laser beam propagation direction in fully transparent entangled solutions of common homopolymers featuring sufficiently high molecular mass and optical anisotropy along the chain backbone. The resulting formation of long-lived stringlike or dotlike patterns on the micrometer scale, probed by dark-field coherent imaging, depends on the molecular mass, architecture, solvent nature, and polymer concentration. Electrostrictive and alignment forces as well as chain cooperativity are responsible for the osmotic compression of the polymer solute. Subsequent waveguiding effects induce autoamplification and "pattern writing" upon prolonged illumination. This wave-medium coupling could potentially lead to photorefractive, microoptics, and nanotechnology applications.

Dynamics of Polymer Interdiffusion: The Ripple Experiment.

We explore the interdiffusion of oppositely labeled triblock polystyrene chains, HDH/DHD, during welding in the melt using dynamic secondary ion mass spectroscopy (DSIMS) and specular neutron reflectivity (SNR). The HDH chains have the central portion of the chain deuterated (D) approximately 50% while the two ends (H) each have approximately 25% protonation; the DHD is oppositely labeled, but each set of chains contains about 50% deuteration. During welding, the deuterium depth profile exhibits "ripples" whose characteristic features, such as the time and molecular weight dependent shape, amplitude, and position, are very sensitive to the microscopic details of the polymer dynamics. The ripple experiment is especially sensitive to the presence, or absence, of topological constraints and anisotropic motion of chains. The current work significantly extends the molecular weight range up to 400 000. This allows greater separation of the six key ripple features used in deciphering the correct polymer dynamics model at the polymer-polymer interface. The DSIMS and SNR experimental results are compared to theoretical predictions and ripple simulations for Rouse, polymer mode-coupling, reptation (with and without tube broadening), and other phenomenological dynamics models. The six ripple characteristics were found to be perfectly correlated and convincingly consistent with the predictions of the reptation dynamics model. The ripple results are in significant disagreement with the polymer mode-coupling model proposed by Schweizer and other tubeless models. We conclude that the reptation model, proposed by DeGennes in 1971 with parallel developments by Edwards, is the correct model to describe the dynamics of polymer interdiffusion.