Synthesis of stable “gold nanoparticle–polymeric micelle” conjugates: A new class of star “molecular chimera” that self‐assemble into linear arrays of spherical micelles

Stable and aggregation‐free “gold nanoparticle–polymeric micelle” conjugates were prepared using a new and simple protocol enabled by the hydrogen bonding between surface‐capping ligands and polymeric micelles. Individual gold nanoparticles were initially capped using a phosphatidylthio–ethanol lipid and further conjugated with a star poly(styrene‐block‐glutamic acid) copolymer micelle using a one‐pot preparation method. The morphology and stability of these gold–polymer conjugates were characterized using transmission electron microscopy (TEM) and UV–vis spectroscopy. The self‐assembly of this class of polymer‐b‐polypeptide in aqueous an medium to form spherical micelles and further their intermicelle reorganization to form necklace‐like chains was also investigated. TEM and laser light scattering techniques were employed to study the morphology and size of these micelles. Polymeric micelles were formed with diameters in the range of 65–75 nm, and supermicellular patterns were observed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3570–3579, 2007     

Tuning of the Temperature Window for Unit‐Cell and Pore‐Size Enlargement in Face‐Centered‐Cubic Large‐Mesopore Silicas Templated by Swollen Block Copolymer Micelles

The unit‐cell size and pore diameter as functions of temperature are investigated in the syntheses of FDU‐12 silicas with face‐centered cubic structure templated by Pluronic (PEO‐PPO‐PEO) block copolymer micelles swollen by toluene. The temperature range in which the unit‐cell size and pore size strongly increase as temperature decreases is correlated with the critical micelle temperature (CMT) of the surfactant. While Pluronic F127 affords a wide range of unit‐cell parameters (28–51 nm) and pore diameters (16–32 nm), it renders moderately enlarged pore sizes at 25 °C. The use of Pluronic F108 with higher CMT affords FDU‐12 with very large unit‐cell size (～49 nm) and large pore diameter (27 nm) at 23 °C. Large unit‐cell size (40–41 nm) and pore size (22 nm) were obtained even at 25 °C. The application of Pluronics F87 and F88 with much smaller molecular weights and higher CMTs also allows one to synthesize FDU‐12 with quite large unit‐cell parameters and pore sizes at room temperature. The present work demonstrates that one can judiciously select Pluronic surfactants with appropriate CMT to shift the temperature range in which the pore diameter is readily tunable.     

The polymerization of acrylonitrile in miniemulsions: “Crumpled latex particles” or polymer nanocrystals

Stable dispersions of polyacrylonitrile (PAN) nanoparticles in the size range between 100 nm < d < 180 nm were made by polymerization in miniemulsion and characterized by dynamic light scattering, transmission electron microscopy (TEM), and wide angle X‐ray scattering (WAXS). Due to the insolubility of the polymer in its monomer, such particles are not accessible by classical emulsion polymerization. The pure PAN particles are composed of ca. 10 nm large polymer nanocrystals, i. e., the formed polymer precipitates and crystallizes direct after formation. As a consequence, the final latexes do not adopt spherical shape, but show a well defined, narrowly distributed boulder‐like phenotype which is called “crumpled latexes”. Copolymerization with styrene results in a continuous transition between the crumpled and a smooth spherical morphology, which is again related to a decreased degree of crystallinity.     

Preparation of magnetic polystyrene latex via the miniemulsion polymerization technique

Magnetic iron oxide (magnetite, Fe₃O₄) nanoparticles were encapsulated with polystyrene to give a stable water‐based magnetic polymer latex, using the miniemulsion polymerization technique. The resulting magnetic latexes were characterized with transmission electron microscopy (TEM), dynamic light scattering (DLS), vibrating sample magnetometer measurements (VSM), and ⁵⁷Fe Mössbauer spectroscopy measurements. TEM revealed that all magnetite nanoparticles were embedded in the polymer spheres, leaving no empty polystyrene particles. The distribution of magnetite particles within the polystyrene spheres was inhomogeneous, showing an uneven polar appearance. The DLS measurements indicated a bimodal size distribution for the particles in the latexes. According to our magnetometry and Mössbauer spectroscopy data, the encapsulated magnetite particles conserve their superparamagnetic feature when they are separated in the polymer matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4802–4808, 2004     

Preparation of poly(styrene‐b‐N‐isopropylacrylamide) micelles surface‐linked with gold nanoparticles and thermo‐responsive ultraviolet–visible absorbance

Poly(styrene‐b‐N‐isopropylacrylamide) (PSt‐b‐PNIPAM) with dithiobenzoate terminal group was synthesized by reversible addition‐fragmentation‐transfer polymerization. The dithiobenzoate terminal group was converted into thiol terminal group with NaBH₄, resulting thiol‐terminated PSt‐b‐PNIPAM‐SH. After PSt‐b‐PNIPAM‐SH assembled into core‐shell micelles in aqueous solution, gold nanoparticles were in situ surface‐linked onto the micelles through the reduction of gold precursor anions with NaBH₄. Thus, temperature responsive core/shell micelles of PSt‐b‐PNIPAM surface‐linked with gold nanoparticles (PSt‐b‐PNIPAM‐Au micelles) were obtained. Transmission Electron Microscopy revealed the successful linkage of gold nanoparticles and the dependence of the number of gold nanoparticles per micelle on the molar ratio of HAuCl₄ to thiol group of PSt‐b‐PNIPAM. Dynamic Light Scattering analysis demonstrated thermo‐responsive behavior of PSt‐b‐PNIPAM‐Au micelles. Changing the temperature of PSt‐b‐PNIPAM‐Au micelles led to the shrinkage of PNIPAM shell and allowed to tune the distance between gold nanoparticles. Ultraviolet–visible (UV–vis) spectroscopy clearly showed the reversible modulation of UV–vis absorbance of PSt‐b‐PNIPAM‐Au micelles upon heating and cooling. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5156–5163, 2007     

Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007     

Mixed micelle formation with hydrophobic and hydrophilic Pluronic block copolymers: implications for controlled and targeted drug delivery

Pluronic block copolymers offer affluent phase behavioral characteristics and are extensively investigated for drug delivery applications. Hydrophobic Pluronics produce larger aggregates whereas hydrophilic Pluronics often generate small-sized micelles in aqueous milieu. To overcome the limitations and combine the advantages of different kinds of Pluronics the mixing of such two types of Pluronics is studied here, especially for hydrophobic Pluronic L81 and relatively hydrophilic Pluronic P123. Critical micelle concentration (CMC) of the developed binary mixtures was 0.032 mg/ml as evidenced from pyrene fluorescence spectroscopy and is located in between that of the individual Pluronics. Dynamic light scattering (DLS) showed very small particle sizes (～20 nm) and low polydispersity indices for most of the mixed micelles. Transmission electron microscopy (TEM) demonstrated spherical shape of micelles. Based upon the ratio of hydrophobic and hydrophilic Pluronics, dispersions of varied stability were obtained. With 0.1/1.0 wt.% and 0.5/3.0 wt.% of Pluronic L81/P123, stable dispersions were obtained. Stability was assessed from turbidity measurement, size analysis and clarity of dispersion on standing. Micelles were also found to be stable in bovine serum albumin (BSA) solution. Mixed micelles showed fairly high entrapment efficiency, loading capacity and sustained release profile for aceclofenac (Acl), a model hydrophobe. Presence of salt lowered Acl solubilization in micelles. Thermodynamic parameters for Acl solubilization in mixed micelles revealed high partition coefficient values and spontaneity of drug solubilization. Thus, the developed novel mixed micelles hold promise in controlled and targeted drug delivery owing to their very small size, high entrapment efficiency and stability.     

Synthesis of Spin‐Crossover Nano‐ and Micro‐objects in Homogeneous Media

New methods are proposed for the synthesis of spin‐crossover nano‐ and micro‐objects. Several nano‐objects that are based upon the spin‐crossover complex [Fe(hptrz)₃](OTs)₂ (hptrz=4‐heptyl‐1,2,4‐triazole, Ts=para‐toluenesulfonyl) were prepared in homogeneous media. The use of various reagents (Triton X‐100, PVP, TOPO, and PEGs of different molecular weights) as stabilizing agents yielded materials of different size (6 nm–2 μm) and morphology (nanorods, nanoplates, small spherical particles, and nano‐ and micro‐crystals). In particular, when Triton X‐100 was used, a variation in the morphology from nanorods to nanoplates was observed by changing the nature of the solvent. Interestingly, the preparation of the nanorods and nanoplates was always accompanied by the formation of small spherical particles. Alternatively, when PEG was used, 200–400 nm crystals of the complex were obtained. In addition, a very promising polymer‐free synthetic method is discussed that was based on the preparation of relatively stable Fe^II–triazole oligomers in CHCl₃. Their specific treatment led to micro‐crystals, small nanoparticles, or gels. The size and morphology of all of these objects were characterized by TEM and by dynamic light scattering (DLS) where possible. Their spin‐crossover behavior was studied by optical and magnetic measurements. The spin‐transition features for large particles (>100 nm) were very similar to that of the bulk material, that is, close to room temperature with a hysteresis width of up to 8 K. The effects of the matrix and/or size‐reduction led to modification of the transition temperature and an abruptness of the spin transition for oligomeric solutions and small nanoparticles of 6 nm in size.     

Synthesis of gold–poly(methyl methacrylate) core–shell nanoparticles by surface‐confined atom transfer radical polymerization at elevated temperature

Surface‐confined atom transfer radical polymerization was used to prepare gold nanoparticle–poly(methyl methacrylate) core–shell particles at elevated temperature. First, gold nanoparticles were prepared by the one‐pot borohydride reduction of tetrachloroaurate in the presence of 11‐mercapto‐1‐undecanol (MUD). MUD‐capped gold nanoparticles were then exchanged with 3‐mercaptopropyltrimethoxysilane (MPS) to prepare a self‐assembled monolayer (SAM) of MPS on the gold nanoparticle surfaces and subsequently hydrolyzed with hydrochloric acid. The extent of exchange of MUD with MPS was determined by NMR. The resulting crosslinked silica‐primer layer stabilized the SAM of MPS and was allowed to react with the initiator [(chloromethyl)phenylethyl] trimethoxysilane. Atom transfer radical polymerization was conducted on the Cl‐terminated gold nanoparticles with the CuCl/2,2′‐bipyridyl catalyst system at elevated temperature. The rates of polymerization with the initiator‐modified gold nanoparticles exhibited first‐order kinetics with respect to the monomer, and the number‐average molecular weight of the cleaved graft polymer increased linearly with the monomer conversion. The presence of the polymer on the gold nanoparticle surface was identified by Fourier transform infrared spectroscopy and transmission electron microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3631–3642, 2005     

Self‐assembly of amphiphilic tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers

Amphiphilic tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers consisting of one polystyrene block and two poly(N‐isopropylacrylamide) blocks were prepared by the “arm‐first” method in which RAFT polymerization and nonconvalent ligand–metal complexation were employed. The prepared amphiphilic star‐shaped metallopolymers are able to form micelles in water. The size and distribution of the micelles were studied by dynamic light scattering and transmission electron microscopy techniques. Preliminary studies indicate that the polymer concentration and the hydrophilic poly(N‐isopropylacrylamide) block length can affect the morphologies of the formed metal‐interfaced core–shell micelles in water. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4204–4210, 2007     

A Simple Protocol to Stabilize Gold Nanoparticles using Amphiphilic Block Copolymers: Stability Studies and Viable Cellular Uptake

Di‐ and triblock non‐ionic copolymers based on poly(ethylene oxide) and poly(propylene oxide) were studied for the stabilization of nanoparticles in water at high ionic strength. The effect of the molecular architecture (di‐ vs. triblock) of these amphiphilic copolymers was investigated by using gold nanoparticles (AuNPs) as probes for colloidal stability. The results demonstrate that both di‐ and triblock copolymers can provide long term stability, and that in both cases AuNPs are individually embedded within globules of polymers. However, in the case of diblock copolymers, the colloidal stability was related to the formation of micelles, in contrast with the case of triblock copolymers, which were previously shown to provide good stability even at concentrations at which micelles do not form. Quartz crystal microbalance (QCM) experiments showed that the presence of the hydrophobic block in the structure of the polymer is important to ensure quantitative adsorption upon a gold surface and to limit desorption. We demonstrate that with an appropriate choice of polymer, the polymer/AuNP hybrids can also undergo filtration and freeze‐drying without noticeable aggregation, which can be very convenient for further applications. Finally, preliminary studies of the cytotoxicity effect on fibroblast cells show that the polymer/AuNP hybrids were not cytotoxic. TEM micrographs on ultrathin sections of cells after incubation with the colloidal solutions show that the nanoparticles were internalized into the cells, conserving their initial size and shape.     

Design of polymeric stabilizers for size-controlled synthesis of monodisperse gold nanoparticles in water

A new methodology is described for the one-step aqueous preparation of highly monodisperse gold nanoparticles with diameters below 5 nm using thioether- and thiol-functionalized polymer ligands. The particle size and size distribution was controlled by subtle variation of the polymer structure. It was shown that poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) were the most effective stabilizing polymers in the group studied and that relatively low molar mass ligands (approximately 2500 g/mol) gave rise to the narrowest particle size distributions. Particle uniformity and colloidal stability to changes in ionic strength and pH were strongly affected by the hydrophobicity of the ligand end group. "Multidentate" thiol-terminated ligands were produced by employing dithiols and tetrathiols as chain-transfer agents, and these ligands gave rise to particles with unprecedented control over particle size and enhanced colloidal stability. It was found throughout that dynamic light scattering (DLS) is a very useful corroboratory technique for characterization of these gold nanoparticles in addition to optical spectroscopy and TEM.     

Polystyrene‐Core–Silica‐Shell Hybrid Particles Containing Gold and Magnetic Nanoparticles

Polystyrene‐core–silica‐shell hybrid particles were synthesized by combining the self‐assembly of nanoparticles and the polymer with a silica coating strategy. The core–shell hybrid particles are composed of gold‐nanoparticle‐decorated polystyrene (PS‐AuNP) colloids as the core and silica particles as the shell. PS‐AuNP colloids were generated by the self‐assembly of the PS‐grafted AuNPs. The silica coating improved the thermal stability and dispersibility of the AuNPs. By removing the “free” PS of the core, hollow particles with a hydrophobic cage having a AuNP corona and an inert silica shell were obtained. Also, Fe₃O₄ nanoparticles were encapsulated in the core, which resulted in magnetic core–shell hybrid particles by the same strategy. These particles have potential applications in biomolecular separation and high‐temperature catalysis and as nanoreactors.     

Magnetic poly(glycidyl methacrylate) particles prepared in the presence of surface‐modified γ‐Fe2O3

Maghemite (γ‐Fe₂O₃) colloid has been synthesized by coprecipitation of ferrous and ferric salts in alkaline medium and oxidation. The obtained nanoparticles were complexed with a phosphate macromonomer—penta(propylene glycol) methacrylate phosphate (PPGMAP). Complexes with the weight ratio PPGMAP/γ‐Fe₂O₃ 0.01–10 were investigated using a range of characterization methods. The amount of PPGMAP attached to the particles was about 22 wt %. The size and size distribution of the γ‐Fe₂O₃ core particles in the dry state was measured by TEM. To complete the TEM images, the hydrodynamic size of the nanoparticles including polymer shell and the maghemite core was determined by DLS measurements in toluene. Magnetic poly(glycidyl methacrylate) (PGMA) nanospheres were obtained by Kraton G 1650‐stabilized and 2,2′‐azobisisobutyronitrile‐initiated polymerization of glycidyl methacrylate (GMA) in toluene or toluene/cyclohexane mixture in the presence of PPGMAP‐coated γ‐Fe₂O₃ colloid. The effect of Kraton G 1650 concentration on the morphology, PGMA nanosphere size and polydispersity was investigated. The particles were characterized also by both thermogravimetric analysis and magnetic measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4982–4994, 2009     

Amphiphilic β‐cyclodextrin‐based star‐like block copolymer unimolecular micelles for facile in situ preparation of gold nanoparticles

Multifunctional polymer unimolecular micelles, which are used as templates to fabricate stable gold nanoparticles (GNPs) in one‐step without external reductant, have been designed and prepared. Amphiphilic 21‐arm star‐like block copolymers β‐cyclodextrin‐{poly(lactide)‐poly(2‐(dimethylamino) ethyl methacrylate)‐poly[oligo(2‐ethyl‐2‐oxazoline)methacrylate]}₂₁ [β‐CD‐(PLA‐PDMAEMA‐PEtOxMA)₂₁] and the precursors are synthesized by the combination of ring‐opening polymerization (ROP) and activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). The tertiary amine groups of PDMAEMA block reduce the counterion to zerovalent gold in situ, and these gold atoms combine mutually to form final GNPs. GNPs with relatively small size and narrow size distribution can be obtained in longer DMAEMA block copolymer, larger molar ratio of DMAEMA to HAuCl₄ and smaller absolute concentrations of both polymer and HAuCl₄. These results showed that the unimolecular micelles can be used as templates for preparing and stabilizing GNPs in situ without any external reducing agents and organic solvents, suggesting that the nanocomposite systems are latent nanocarriers for further biomedical application. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 186–196     

Influence of Gold Nanoparticles of Varying Size in Improving the Lipase Activity within Cationic Reverse Micelles

Herein, we report the effect of gold nanoparticles (GNPs) in enhancing lipase activity in reverse micelles of cetyltrimethylammonium bromide (CTAB)/water/isooctane/n‐hexanol. The size and concentration of the nanoparticles were varied and their specific roles were assessed in detail. An overall enhancement of activity was observed in the GNP‐doped CTAB reverse micelles. The improvement in activity becomes more prominent with increasing concentration and size of the GNPs (0–52 μM and ca. 3–30 nm, respectively). The observed highest lipase activity (k₂=1070±12 cm³ g^?1 s^?1) in GNP‐doped CTAB reverse micelles ([GNP]: 52 μm, ca. 20 nm) is 2.5‐fold higher than in CTAB reverse micelles without GNPs. Improvement in the lipase activity is only specific to the GNP‐doped reverse micellar media, whereas GNP deactivates and structurally deforms the enzyme in aqueous media. The reason for this activation is probably due to the formation of larger‐sized reverse micelles in which the GNP acts as a polar core and the surfactants aggregate around the nanoparticle (‘GNP pool’) instead of only water. Lipase at the augmented interface of the GNP‐doped reverse micelle showed improved activity because of enhancement in both the substrate and enzyme concentrations and increased flexibility in the lipase conformation. The extent of the activation is greater in the case of the larger‐sized GNPs. A correlation has been established between the activity of lipase and its secondary structure by using circular dichroism and FTIR spectroscopic analysis. The generalized influence of GNP is verified in the reverse micelles of another surfactant, namely, cetyltripropylammonium bromide (CTPAB). TEM, dynamic light scattering (DLS), and UV/Vis spectroscopic analysis were utilized to characterize the GNPs and the organized aggregates. For the first time, CTAB‐based reverse micelles have been found to be an excellent host for lipase simply by doping with appropriately sized GNPs.     

Synthesis,thermo-responsive micellization and caffeine drug release of novel PBMA-<Emphasis Type="Italic">b</Emphasis>-PNIPAAm block polymer brushes

Brush-like block copolymers with poly(t-butyl methacrylate) (PBMA) and poly(N-isopropylacrylamide) (PNIPAAm) as side arms, PBMA-b-PNIPAAm, were designed and synthesized via a simple free radical polymerization route. The chemical structure and molecular weight of these polymer brushes were characterized and determined by nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectrometry (FTIR) and gel permeation chromatography (GPC). The micellar formation by these polymer brushes in aqueous solutions were detected by a surface tension technique, and the critical micelle concentration (CMC) ranged from 1.53 to 8.06 mg L⁻¹. The morphology and geometry of polymer micelles were investigated by transmission electron microscope (TEM) and dynamic light scattering (DLS). The polymer micelles assume the regularly-spherical core-shell structure with well-dispersed individual nanoparticles, and the particle size was in the range from 36 to 93 nm. The PNIPAAm segments exhibited a thermoreversible phase transition, so the resulting block polymer brushes were temperature-sensitive and the low critical solution temperature (LCST) was determined by UV-vis spectrometer at about 28.82–29.40°C. The characteristic parameters of the polymer micelles such as CMC, micellar size and LCST values were affected by their compositional ratios and the length of hydrophilic or hydrophobic chains. The evaluation for caffeine drug release behavior of the block polymer micelles demonstrated that the self-assembled micelles exhibited thermal-triggered properties in controlled drug release.     

Synthesis and characterization of micron‐sized monodisperse superparamagnetic polymer particles with amino groups

Micron‐sized monodisperse superparamagnetic polyglycidyl methacrylate (PGMA) particles with functional amino groups were prepared by a process involving: (1) preparation of parent monodisperse PGMA particles by the dispersion polymerization method, (2) chemical modification of the PGMA particles with ethylenediamine (EDA) to yield amino groups, and (3) impregnation of iron ions (Fe²⁺ and Fe³⁺) inside the particles and subsequently precipitating them with ammonium hydroxide to form magnetite (Fe₃O₄) nanoparticles within the polymer particles. The resultant magnetic PGMA particles with amino groups were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X‐ray diffractometry (XRD), and vibrating sample magnetometry (VSM). SEM showed that the magnetic particles had an average size of 2.6 μm and were highly monodisperse. TEM demonstrated that the magnetite nanoparticles distributed evenly within the polymer particles. The existence of amino groups in the magnetic polymer particles was confirmed by FTIR. XRD indicated that the magnetic nanoparticles within the polymer were pure Fe₃O₄ with a spinel structure. VSM results showed that the magnetic polymer particles were superparamagnetic, and saturation magnetization was found to be 16.3 emu/g. The Fe₃O₄ content of the magnetic particles was 24.3% based on total weight. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3433–3439, 2005     

Preparation and properties of ionically cross‐linked chitosan nanoparticles

Chitosan nanoparticles were fabricated by a method of tripolyphosphate (TPP) cross‐linking. The influence of fabrication conditions on the physical properties and drug loading and release properties was investigated by transmission electron microscopy (TEM), dynamic light scattering (DLS), and UV–vis spectroscopy. The nanoparticles could be prepared only within a zone of appropriate chitosan and TPP concentrations. The particle size and surface zeta potential can be manipulated by variation of the fabrication conditions such as chitosan/TPP ratio and concentration, solution pH and salt addition. TEM observation revealed a core–shell structure for the as‐prepared nanoparticles, but a filled structure for the ciprofloxacin (CH) loaded particles. Results show that the chitosan nanoparticles were rather stable and no cytotoxicity of the chitosan nanoparticles was found in an in vitro cell culture experiment. Loading and release of CH can be modulated by the environmental factors such as solution pH and medium quality. Copyright © 2008 John Wiley & Sons, Ltd.     

Effects of Pluronics surfactants on morphology and porosity of hematite particles produced from forced hydrolysis reaction

The shape and porosity of hematite particles, produced from a forced hydrolysis reaction of acidic FeCl₃ solution, were controlled by using Pluronics as nonionic surfactants (0–4 wt.%). Pluronics possess a nominal formula of (PEO) _x –(PPO) _y –(PEO) _x . The effect of Pluronics with low hydrophilicity (PEO contents were less than 50 mol%) was small and provided spherical particles the same as that of the system without Pluronics (control system). However, Pluronics with higher hydrophilicity (PEO contents were over 50 mol%) gave ellipsoidal hematite particles. This effect on the particle morphology was enhanced by an increase in their molecular weight. On the other hand, the Pluronics possessing an opposite nominal formula [(PPO) _x –(PEO) _y –(PPO) _x ] exhibited no effect on the particle shape; it only depressed phase transformation from ?-FeOOH to hematite. Not only the morphology but also the pore size of hematite particles was controlled from nonporous to mesoporous by using Pluronics. The N₂ adsorption experiment and t-plot curve analysis revealed that the hematite particles changed from mesoporous to microporous by an increase in the concentration of Pluronics. On the other hand, in the presence of very low amounts of Pluronics molecules (0.1 wt.%), nonporous hematite particles were produced via strong aggregation of PN particles by their hydrogen bonding between hydroxyl and PEO or PPO groups. The dynamic light scattering measurement for the system with Pluronics clarified the existence of polynuclear (PN) particles with a hydrodynamic particle diameter (D _a) of ca. 40 nm after these were aged for 6 h. The size of PN particles remained constant at ca. 40 nm during aging time of 12 h～3 days, but the scattering intensity was decreased. This decrease in the scattering intensity reveals that the number of PN particles is reduced by aggregation. The transmission electron microscope, inductively coupled plasma atomic emission spectroscopy, and total organic carbon analysis measurements employed on the systems produced for ellipsoidal particles elucidated that the formation of ellipsoidal hematite particles is attributed to the adsorption of Pluronics on the surfaces of PN and growing hematite particles.