Influence of hydrophilic block length on the aggregation properties of polyglycidol-polystyrene-polyglycidol copolymers.

Amphiphilic triblock copolymers, polyglycidol-polystyrene-polyglycidol (PGL-PS-PGL), were synthesised via anionic polymerization starting from the synthesis of a polystyrene macroinitiator with 60 styrene units in the block terminated by ethylene oxide. Poly(ethoxyethyl glycidyl ether) blocks of different lengths were created on both sides of the macroinitiator. By removing the ethoxyethyl blocking groups, PGL-PS-PGL copolymers containing polyglycidol blocks with DP 11, 23, 44 and 63 were received. Their structures were determined by NMR and FTIR. The hydrophilicity of PLG-PS-PGL films was studied upon exposure to water vapour. To perform the copolymers' aggregation in water, the samples were dialysed from DMF into water. The critical concentration of their micellisation (CMC) was determined by measuring the absorbance of the 1,6-diphenylhexa-1,3,5-triene (DPH) probe and the intensity of light scattered by the copolymers' solution as a function of concentration. CMC values increased with increasing the number of hydrophilic glycidol units in the copolymer chain. The sizes of aggregates formed slightly above the critical concentration were measured by dynamic light scattering (DLS), and particles were imaged by cryo-TEM. Cryo-TEM pictures showed the presence of regular micelles in copolymer dispersions. For copolymers with shorter PGL chains aggregated partices were detected. Moreover, cryo-TEM demonstrated that the copolymers with a polyglycidol block of DP = 63 formed regular spherical micelles that formed 2D ordered organisation on the surface. X-ray measurements showed the formation of a partially crystallised PS core in the micelle's interior. The aggregates of all copolymers were stable. Their sizes did not change after one year of storage. The particles did not disassociate even after diluting their dispersions to a concentration 10 times lower than the critical concentration.

New Class of Polymer Materials-Quasi-Nematic Colloidal Particle Self-Assemblies: The Case of Assemblies of Prolate Spheroidal Poly(Styrene/Polyglycidol) Particles.

Assemblies of colloidal polymer particles find various applications in many advanced technologies. However, for every type of application, assemblies with properly tailored properties are needed. Until now, attention has been concentrated on the assemblies composed of spherical particles arranged into so-called perfect colloidal crystals and on complex materials containing mixtures of crystal and disordered phases. However, new opportunities are opened by using assemblies of spheroidal particles. In such assemblies, the particles, in addition to the three positional have three angular degrees of freedom. Here, the preparation of 3D assemblies of reference microspheres and prolate spheroidal poly(styrene/polyglycidol) microparticles by deposition from water and water/ethanol media on silicon substrates is reported. The particles have the same polystyrene/polyglycidol composition and the same volumes but differ with respect to their aspect ratio (AR) ranged from 1 to 8.5. SEM microphotographs reveal that particles in the assembly top layers are arranged into the quasi-nematic structures and that the quality of their orientation in the same direction increase with increasing AR. Nano- and microindentation studies demonstrate that interactions of sharp and flat tips with arrays of spheroidal particles lead to different types of particle deformations.

Synthesis, Hydrophilicity and Micellization of Coil-Brush Polystyrene-b-(polyglycidol-g-polyglycidol) Copolymer-Comparison with Linear Polystyrene-b-polyglycidol.

In this paper, an original method of synthesis of Coil-Brush amphiphilic polystyrene-b-(polyglycidol-g-polyglycidol) (PS-b-(PGL-g-PGL)) block copolymers was developed. The hypothesis that their hydrophilicity and micellization can be controlled by polyglycidol blocks architecture was verified. The research enabled comparison of behavior in water of PS-b-PGL copolymers and block-brush copolymers PS-b-(PGL-g-PGL) with similar composition. The Coil-Brush copolymers were composed of PS-b-PGL linear core with average DPn of polystyrene 29 and 13 of polyglycidol blocks. The DPn of polyglycidol side blocks of coil-b-brush copolymers were 2, 7, and 11, respectively. The copolymers were characterized by 1H and 13C NMR, GPC, and FTIR methods. The hydrophilicity of films from the linear and Coil-Brush copolymers was determined by water contact angle measurements in static conditions. The behavior of Coil-Brush copolymers in water and their critical micellization concentration (CMC) were determined by UV-VIS using 1,6-diphenylhexa-1,3,5-trien (DPH) as marker and by DLS. The CMC values for brush copolymers were much higher than for linear species with similar PGL content. The results of the copolymer film wettability and the copolymer self-assembly studies were related to fraction of hydrophilic polyglycidol. The CMC for both types of polymers increased exponentially with increasing content of polyglycidol.

Anti-Inflammatory Effect of Very High Dose Local Vessel Wall Statin Administration: Poly(L,L-Lactide) Biodegradable Microspheres with Simvastatin for Drug Delivery System (DDS).

Atherosclerosis involves an ongoing inflammatory response of the vascular endothelium and vessel wall of the aorta and vein. The pleiotropic effects of statins have been well described in many in vitro and in vivo studies, but these effects are difficult to achieve in clinical practice due to the low bioavailability of statins and their first-pass metabolism in the liver. The aim of this study was to test a vessel wall local drug delivery system (DDS) using PLA microstructures loaded with simvastatin. Wistar rats were fed high cholesterol chow as a model. The rat vessels were chemically injured by repeated injections of perivascular paclitaxel and 5-fluorouracil. The vessels were then cultured and treated by the injection of several concentrations of poly(L,L-lactide) microparticles loaded with the high local HMG-CoA inhibitor simvastatin (0.58 mg/kg) concentration (SVPLA). Histopathological examinations of the harvested vessels and vital organs after 24 h, 7 days and 4 weeks were performed. Microcirculation in mice as an additional test was performed to demonstrate the safety of this approach. A single dose of SVPLA microspheres with an average diameter of 6.4 µm and a drug concentration equal to 8.1% of particles limited the inflammatory reaction of the endothelium and vessel wall and had no influence on microcirculation in vivo or in vitro. A potent pleiotropic (anti-inflammatory) effect of simvastatin after local SVPLA administration was observed. Moreover, significant concentrations of free simvastatin were observed in the vessel wall (compared to the maximum serum level). In addition, it appeared that simvastatin, once locally administered as SVPLA particles, exerted potent pleiotropic effects on chemically injured vessels and presented anti-inflammatory action. Presumably, this effect was due to the high local concentrations of simvastatin. No local or systemic side effects were observed. This approach could be useful for local simvastatin DDSs when high, local drug concentrations are difficult to obtain, or systemic side effects are present.

Functionalized Particles Designed for Targeted Delivery.

Pure bioactive compounds alone can only be exceptionally administered in medical treatment. Usually, drugs are produced as various forms of active compounds and auxiliary substances, combinations assuring the desired healing functions. One of the important drug forms is represented by a combination of active substances and particle-shaped polymer in the nano- or micrometer size range. The review describes recent progress in this field balanced with basic information. After a brief introduction, the paper presents a concise overview of polymers used as components of nano- and microparticle drug carriers. Thereafter, progress in direct synthesis of polymer particles with functional groups is discussed. A section is devoted to formation of particles by self-assembly of homo- and copolymer-bearing functional groups. Special attention is focused on modification of the primary functional groups introduced during particle preparation, including introduction of ligands promoting anchorage of particles onto the chosen living cell types by interactions with specific receptors present in cell membranes. Particular attention is focused on progress in methods suitable for preparation of particles loaded with bioactive substances. The review ends with a brief discussion of the still not answered questions and unsolved problems.

Chitosan-polyglycidol complexes to coating iron oxide particles for dye adsorption.

The study sheds light on the interaction between chitosan (Ch) and polyglycidol (PGL) and uses their interpolymer complex in hydrophilic coating of iron oxide particles (M). Preliminary investigations were performed by modeling chitosan and polyglycidol chains interactions using coarse grained beads approximation and molecular dynamics simulations. The results revealed that Ch and PGL chains associate together forming weak strength complexes, which was experimentally confirmed by surface tension, fluorescence and FTIR. The Ch-PGL mixture (C) and sodium dodecylsulfate (S) were used for layer-by-layer preparation of hydrophilic multilayer coatings of M. The successful covering, demonstrated by DLS, Zeta potential, FTIR, EDAX, preserved the particles super-paramagnetic properties. The most stable multilayer nanocomposite (MSCS) efficiently adsorbed methylene blue from water. The Freundlich model fitted well the equilibrium isotherm data, indicating a heterogeneous, multilayer adsorption. Benefiting from both nano-size and magnetic properties, this adsorbent could be an effectively, cheaply and eco-friendly wastewater treatment means.

Micellization of Polystyrene-b-Polyglycidol in Dioxane and Water/Dioxane Solutions.

In this work, the self-assembly of a series of amphiphilic polystyrene-b-polyglycidol (PS-b-PGL) diblock copolymers in dioxane and dioxane/water mixtures is presented. The PS-b-PGL have an average degree of polymerization (DP) of PS block equal to 29 units and varied degrees of polymerization for the glycidol segments with DPs of 13, 42, 69 and 117. In dioxane, amphiphilic diblock copolymers form micelles with the hydrophilic PGL placed in the core. Critical micelle concentration (CMC) was determined based on the intensity of scattered light vs. concentration. The micelle size was measured by dynamic light scattering and transmission electron microscopy. Also, the behaviour of the copolymer was studied in water/dioxane solutions by following the changes of scattered light intensity with the addition of water to the system. Critical water content (CWC) of the studied systems decreased as the initial PS-b-PGL concentration in dioxane increased. This process was accompanied by a decrease in the size of aggregate formed. For a given initial copolymer concentration, the size of copolymer aggregates decreased linearly with increasing the length of the PGL block.

Adsorption and covalent binding of fibrinogen as a method for probing the chemical composition of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microsphere surfaces.

We investigated the distribution of polyglycidol and polystyrene on the surface of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microspheres (random distribution or segregated into hydrophilic and hydrophobic patches), using fibrinogen (Fb) as a macromolecular probe. The fibrinogen was adsorbed or covalently attached to the surface of the poly(styrene-co-α-tert-butoxy-ω-vinylbenzyl-polyglycidol) (P(S/PGLy)) microspheres. The P(S/PGLy) particles were prepared by emulsion copolymerization of styrene and α-tert-butoxy-ω-vinylbenzyl-polyglycidol (PGLy) macromonomer initiated with potassium persulfate. The polymerizations yielded P(S/PGLy) particles with various surface fractions of polyglycidol, depending on the amount of added macromonomer and the addition process. In some syntheses, the entire macromonomer amount was added once at the beginning of the polymerization, while in others, the macromonomer was added gradually after the formation of particle seeds from pure polystyrene. XPS studies revealed that the fraction of polyglycidol in the interfacial layer of the microspheres was larger when the entire amount of macromonomer was added at the beginning of the polymerization than when it was added after formation of the polystyrene seeds. Studies of fibrinogen adsorption provided the first evidence of segregation of the hydrophobic (polystyrene) and hydrophilic (polyglycidol) components at the surface of the composite P(S/PGLy) microspheres into patches. The hydrophobic patches are composed mainly of polystyrene. However, they also contain a small amount of polyglycidol chains, making the adsorption of fibrinogen weaker than the adsorption onto the pure polystyrene. Studies of covalent immobilization of fibrinogen on the microspheres via 1,3,5-trichlorotriazine confirmed these findings.

Size-Controlled 3D Colloidal Crystals Formed in an Aqueous Suspension of Polystyrene/Polyglycidol Microspheres with Covalently Bound l-DOPA.

Stable three-dimensional colloidal crystals were fabricated in an aqueous suspension of Tris buffer at pH > 8. The basic building blocks of the crystals were submicron-sized polystyrene-polyglycidol core-shell particles (Dn(SEM) = 270 ± 18 nm) with covalently bound 3,4-dihydroxyphenylalanine (l-DOPA). The growth of the crystals was triggered by a thermodynamically favorable arrangement of particles leading to their close packing and by the formation of covalent cross-links between the individual particles. Under alkaline conditions, molecules of l-DOPA are oxidized, which allows their participation in cross-linking, necessary for the stabilization of the formed colloidal crystals. The average size of the fabricated colloidal crystals is determined by their weight, density of the suspending medium, and the energy of their Brownian motion. Crystals generated during the suspension of particles fall down after reaching the critical weight. Therefore, crystals of similar dimensions are deposited at the bottom of the vessel. The described system is the first example of the formation of stable colloidal crystals in a suspension.

Polylactides-Methods of synthesis and characterization.

Polylactides with various molar masses, microstructures and crystallinities are used as degradable and biocompatible polymers suitable for preparation of drug carriers and temporary medical implants. This paper presents state of current knowledge on synthesis of lactic acids, high purity lactide monomers and their polymerization. Syntheses of high molar mass polylactides by polycondensation of lactic acid and by ring-opening polymerization of lactides are described and their advantages and disadvantages are discussed. Mechanisms of lactide polymerization initiated by metal alkoxides are described. There are presented also results of more recent studies of polymerization initiated with the so-called "no metal" organocatalysts; both anionic and cationic. Presented are advantages and limitations of synthesis of PLA by all the major polymerization processes until now. Some properties of PLA and most important methods used for PLA characterization are also described.

Polyglycidol, Its Derivatives, and Polyglycidol-Containing Copolymers-Synthesis and Medical Applications.

Polyglycidol (or polyglycerol) is a biocompatible polymer with a main chain structure similar to that of poly(ethylene oxide) but with a ⁻CH2OH reactive side group in every structural unit. The hydroxyl groups in polyglycidol not only increase the hydrophilicity of this polymer but also allow for its modification, leading to polymers with carboxyl, amine, and vinyl groups, as well as to polymers with bonded aliphatic chains, sugar moieties, and covalently immobilized bioactive compounds in particular proteins. The paper describes the current state of knowledge on the synthesis of polyglycidols with various topology (linear, branched, and star-like) and with various molar masses. We provide information on polyglycidol-rich surfaces with protein-repelling properties. We also describe methods for the synthesis of polyglycidol-containing copolymers and the preparation of nano- and microparticles that could be derived from these copolymers. The paper summarizes recent advances in the application of polyglycidol and polyglycidol-containing polymers as drug carriers, reagents for diagnostic systems, and elements of biosensors.

Gradient Poly(styrene-co-polyglycidol) Grafts via Silicon Surface-Initiated AGET ATRP.

Gradient copolymer grafts of styrene and α-tert-butoxy-ω-vinylbenzyl-poly(glycidol ethoxyethyl ether) (PGLet), a precursor of α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer (PGL), were prepared on silicon wafers via a surface-initiated activator generated by electron transfer radical polymerization (AGET ATRP). Silicon plates with previously attached 2-bromoisobutyrate served as a macroinitiator for the AGET ATRP (activator generated by electron transfer) of styrene and PGLet. The copolymers' gradient P(S-co-PPGL) of composition and thickness was obtained by a simple method where the plates were slowly removed from reaction mixture using a step motor. PGLet was added continuously (dropwise) into the reactor during withdrawal of the plates from solution in order to increase the relative concentration of PGLet in polymerization mixture. A range of strategies of making grafts was tested. The plates with copolymers grafts were analyzed by various techniques, like XPS, ellipsometry, and FTIR spectroscopy. The results indicate that the AGET ATRP process is dependent on the styrene/PGLet macromonomer ratio in the polymerization mixture. Under optimal conditions, the addition of PGLet during polymerization and subsequent deprotection of hydroxyl groups of PGLet permit to obtain plates with a novel copolymer layer with composition, thickness, and wettability gradient. Plates with chemical composition of copolymer grafts gradient served as versatile supports with controlled hydrophilic/hydrophobic area and were suitable for tailored deposition of particles.

Synthesis of a paraffin phase change material microencapsulated in a siloxane polymer.

The coemulsification method suitable for the formulation of microcapsules of n-eicosane coated with a polysiloxane is developed. This method allows to synthesize core-shell microcapsules of paraffin which have the shape of spheres or distorted spheres and are designed for the use as phase change materials. The microcapsules are formed in aqueous phase by the precipitation of n-eicosane together with modified polyhydromethylsiloxane from a common solvent which is miscible with aqueous media. The polysiloxane is modified by the attachment of silylvinyl and alkoxy functions before coemulsification with the paraffin. It also contains the Pt(0) Karstedt catalyst. The microcapsules formed by coemulsification are stabilized by the in situ cross-linking of the polysiloxane shell. The shell is additionally modified by the in situ generation of silanol groups which provide colloidal stabilization of microspheres in aqueous phase. Microcapsules were studied by DSC, SEM, optical polarized microscope, and by thermooptical analysis (TOA).

Effect of surface modification of silica nanoparticles on toxicity and cellular uptake by human peripheral blood lymphocytes in vitro.

Silica nanoparticles have an interesting potential in drug delivery, gene therapy and molecular imaging due to the possibility of tailoring their surface reactivity that can be obtained by surface modification. Despite these potential benefits, there is concern that exposure of humans to certain types of silica nanomaterials may lead to significant adverse health effects. The motivation of this study was to determine the kinetics of cellular binding/uptake of the vinyl- and the aminopropyl/vinyl-modified silica nanoparticles into peripheral blood lymphocytes in vitro, to explore their genotoxic and cytotoxic properties and to compare the biological properties of modified silica nanoparticles with those of the unmodified ones. Size of nanoparticles determined by SEM varied from 10 to 50 nm. The average hydrodynamic diameter and zeta potential also varied from 176.7 nm (+18.16 mV) [aminopropyl/vinyl-modified] and 235.4 nm (-9.49 mV) [vinyl-modified] to 266.3 (-13.32 mV) [unmodified]. Surface-modified silica particles were internalized by lymphocytes with varying efficiency and expressed no cytotoxic nor genotoxic effects, as determined by various methods (cell viability, apoptosis/necrosis, oxidative DNA damage, chromosome aberrations). However, they affected the proliferation of the lymphocytes as indicated by a decrease in mitotic index value and cell cycle progression. In contrast, unmodified silica nanoparticles exhibited cytotoxic and genotoxic properties at high doses as well as interfered with cell cycle.

Progress in nanoparticulate systems for peptide, proteins and nucleic acid drug delivery.

Progress in many therapies, in particular in the therapies based on peptides, proteins and nucleic acids used as bioactive compounds, strongly depends on development of appropriate carriers which would be suitable for controlled delivery of the intact abovementioned compounds to required tissues, cells and intracellular compartments. This review presents last ten years' achievements and problems in development and application of synthetic polymer nanoparticulate carriers for oral, pulmonary and nasal delivery routes of oligopeptides and proteins. Whereas some traditional synthetic polymer carriers are only briefly recalled the main attention is concentrated on nanoparticles produced from functional copolymers mostly with hydroxyl, carboxyl and amino groups, suitable for immobilization of targeting moieties and for assuring prolonged circulation of nanoparticles in blood. Formulations of various nanoparticulate systems are described, including solid particles, polymer micelles, nanovesicles and nanogels, especially systems allowing drug release induced by external stimuli. Discussed are properties of these species, in particular stability in buffers and models of body fluids, loading with drugs and with drug models, drug release processes and results of biological studies. There are also discussed systems for gene delivery with special attention devoted to polymers suitable for compacting nucleic acids into nanoparticles as well as the relations between chemical structure of polymer carriers and ability of the latter for crossing cell membranes and for endosomal escape.

Preparation and optical properties of novel bioactive photonic crystals obtained from core-shell poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microspheres.

Optical properties of polymer microspheres with polystyrene cores and polyglycidol-enriched shells poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) (P(S/PGL) particles with number average diameters D(n) determined by scanning electron microscopy equal 237 and 271 nm), were studied before and after immobilization of ovalbumin. The particles were synthesized by emulsifier-free emulsion copolymerization of styrene and polyglycidol macromonomer (poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol)) initiated with potassium persulfate. Molar fraction of polyglycidol units in the interfacial layer of the microspheres determined by XPS was equal 42.6 and 34.0%, for the particles with D(n) equal 137 and 271 nm, respectively. Colloidal crystals from the aforementioned particles were prepared by deposition of particle suspensions on the glass slides and subsequent evaporation of water. It was found that optical properties of colloidal crystals from the P(S/PGL) microspheres strongly depend on modification of their interfacial layer by covalent immobilization of ovalbumin. The coating of particles with ovalbumin resulted in decreasing their refractive index from 1.58 to 1.52.

Highly hydrophilic surfaces from polyglycidol grafts with dual antifouling and specific protein recognition properties.

Homopolymer grafts from α-tert-butoxy-ω-vinylbenzyl-polyglycidol (PGL) were prepared on gold and stainless steel (SS) substrates modified by 4-benzoyl-phenyl (BP) moieties derived from the electroreduction of the parent salt 4-benzoyl benzene diazonium tetrafluoroborate. The grafted BP aryl groups efficiently served to surface-initiate photopolymerization (SIPP) of PGL. In similar conditions, SIPP of hydroxyethyl methacrylate (HEMA) permitted the production of PHEMA grafts as model surfaces. Water contact angles were found to be 66°, 15°, and 0° for SS-BP, SS-PHEMA, and SS-PPGL, respectively. The spontaneous spreading of water drops on SS-PPGL was invariably observed with 1.5 µL water drops. PPGL thus appears as a superhydrophilic polymer. Resistance to nonspecific adsorption of proteins of PPGL and PHEMA grafts on gold was evaluated by surface plasmon resonance (SPR) using antibovine serum albumin (anti-BSA). The results conclusively show that PPGL-grafts exhibit enhanced resistance to anti-BSA adsorption compared to the well-known hydrophilic PHEMA. PPGL grafts were further modified with BSA through the carbonyldiimidazole activation of the OH groups providing immunosensing surfaces. The so-prepared PPGL-grafted BSA hybrids specifically interacted with anti-BSA in PBS as compared to antimyoglobin. It is clear that the superhydrophilic character of PPGL grafts opens new avenues for biomedical applications where surfaces with dual functionality, namely, specific protein grafting together with resistance to biofouling, are required.

Thermoresponsive colloidal crystals built from core-shell poly(styrene/alpha-tert-butoxy-omega-vinylbenzylpolyglycidol) microspheres.

Core-shell particles of poly(styrene/alpha-tert-butoxy-omega-vinylbenzylpolyglycidol) P(S/PGL) were used as new building blocks for the assembly of a colloidal crystal. The added-value properties of these particles for photonic crystal architectures are their high hydrophilicity together with their thermoresponsivity. Indeed, the poglycidol-rich shell undergoes a phase transition above 45 degrees C, which leads to its collapse at the particle surface accompanied by a decrease in the particle diameter. The three-dimensional crystalline arrays display Bragg diffraction properties, as judged by angle-resolved reflectance spectroscopy. The thermoresponsivity of the colloidal assemblies was observed through modifications of their optical properties with respect to the temperature used during the assembly process. The wetting properties of the crystalline material were also shown to reversibly switch from hydrophilic to hydrophobic as a function of the assembly temperature, thus evidencing the reorganization of the surface polyglycidol chains during the polymer phase transition. This work shows conclusively that P(S/PGL) particles are promising alternatives to poly(N-isopropylacrylamide) and poly(ethylene glycol) particles for the elaboration of thermoresponsive colloidal crystals, with a phase transition situated in between those of these two polymers.

Properties of poly(styrene/alpha-tert-butoxy-omega-vinylbenzyl-polyglycidol) microspheres suspended in water. Effect of sodium chloride and temperature on particle diameters and electrophoretic mobility.

Hydrodynamic and electrophoretic properties of core-shell poly(styrene/alpha- tert-butoxy-omega-vinylbenzyl-polyglycidol) (P(S/PGL)) microspheres suspended in water are described. The microspheres were obtained by surfactant-free emulsion copolymerization of styrene and alpha- tert-butoxy-omega-vinylbenzyl-polyglycidol macromonomer ( M n = 2800, M w/ M n = 1.05). The process yielded microspheres with number average diameter D n = 270 nm and with low diameter dispersity index D w/ D n = 1.01. Shells of P(S/PGL) microspheres were enriched in polyglycidol. Molar fraction of polyglycidol monomeric units in the shells (determined by X-ray photoelectron spectroscopy) was equal to 0.34, which is much higher than the average molar fraction of polyglycidol monomeric units in whole particles of 0.048. Influences of NaCl concentration and temperature on P(S/PGL) microsphere diameters and on their electrophoretic mobility were investigated. It was found that hydrodynamic diameter of P(S/PGL) microspheres, determined by photon correlation spectroscopy, decreased significantly when temperature did exceed a certain value (transition temperature, T t). It has been found that the decrease is more pronounced for higher concentrations of NaCl in the medium. For microspheres suspended in 10 (-1) M NaCl, the hydrodynamic diameter decreased by 8% whereas for the same particles in pure water the diameter decreased by 5.2%. The process of shrinkage was fully reversible. Values of T t for P(S/PGL) microspheres were lower for higher concentrations of NaCl. Adjustment of salt concentration allowed controlling T t in a range from 44.4 to 49.9 degrees C. 13C NMR relaxation time measurements (T 1) for carbon atoms in polyglycidol macromonomer revealed that T 1 did increase with increasing temperature (in temperature range from 25 to 75 degrees C) indicating higher motion of chains at higher temperature. Addition of NaCl did not induce a substantial change of T 1 in the mentioned temperature range. The swelling-deswelling properties of P(S/PGL) microspheres' interfacial layer affected adsorption of P(S/PGL) particles on modified with (3-aminopropyl)triethoxysilane mica. It was shown that the deposition of P(S/PGL) microspheres at 25 degrees C on mica led to formation of two-dimensional crystal-shape assemblies, whereas at 60 degrees C (far above T t = 49.8 degrees C in H2O) the microspheres were randomly adsorbed without formation of colloidal crystal assemblies.

Nanoparticles from polylactide and polyether block copolymers: formation, properties, encapsulation, and release of pyrene--fluorescent model of hydrophobic drug.

Polylactide-b-polyglycidol-b-poly(ethylene oxide) terpolymers and their derivatives with carboxyl and 4-(phenylazo)phenyl labels in polyglycidol blocks were used for formation of nanoparticles. Nanoparticles were produced by self assembly of terpolymer macromolecules in water above the critical aggregation concentration and by dialysis of terpolymer solutions in 1,4-dioxane against water. For terpolymers with 4-(phenylazo)phenyl labels critical aggregation concentrations increased after irradiation with UV light (300 < lambda < 400 nm) inducing conformational change of the label from trans- to cis-conformation. Diameters of nanoparticles obtained by self-assembly of macromolecules ranged from 20 to 44 nm. Dialysis yielded nanoparticles with bimodal diameter distribution. One fraction had diameters below 35 nm and diameters of the second fraction were in a range from 350 to 2300 nm, depending on terpolymer structure. Mixtures of terpolymers with poly(L,L-lactide) and poly(D,D-lactide) blocks yielded nanoparticles with diameters from 350 to 440 nm. Pyrene was incorporated into nanoparticles by partition between solution and nanoparticles or directly during particle formation by dialysis. Monitoring of pyrene release from nanoparticles suggests that a fraction of this compound was entrapped into the polylactide core whereas the remaining one was located in the polyether rich shell. The release from shells is faster for nanoparticles made from copolymers with carboxyl labels in polyglycidol blocks.