Surface initiated ATRP in the synthesis of iron oxide/polystyrene core/shell nanoparticles

A method to prepare magnetic nanoparticles with a covalently bonded polystyrene shell by surface initiated atom transfer radical polymerization (ATRP) was reported. First, the initiator for ATRP was covalently bonded onto the surface of magnetic nanoparticles through our novel method, which was the combination of ligand exchange reaction and condensation of triethoxysilane having an ATRP initiating site, 2-bromo-2-methyl-N-(3-(triethoxysilyl)propyl) propanamide. Then the surface initiated ATRP of styrene mediated by a copper complex was carried out and exhibited the characteristics of a controlled/“living” polymerization. The as-synthesized nanoparticles were coated with well-defined PS of a target molecular weight up to 45 K. These hybrid nanoparticles had an exceptionally good dispersibility in organic solvents and were subjected to detailed characterization using DLS, GPC, FTIR, XPS, UV-vis, TEM and TGA.     

Reverse Atom Transfer Radical Polymerization of MMA in the Presence of CaCO3/SiO2 Two-Component Composite Particles

Summary: We previously discovered that structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO₃/SiO₂ three-component composite particles, can be achieved via reverse atom transfer radical polymerization (ATRP), using 2,2′-azo-bis-isobutyronitrile as initiator and Cu^II bromide as catalyst. In the present study, the influence of the mass ratio of CaCO₃/SiO₂ two-component composite particles to methyl methacrylate (MMA) on the rate and behavior of the polymerization was studied in detail. The results illustrate that increasing the mass ratio of CaCO₃/SiO₂ two-component composite particles will decrease the overall rate of polymerization of MMA under standard reverse ATRP conditions. Thermal properties of the obtained well-defined particles were characterized and determined by thermogravimetric analysis (TGA). The results indicate that well-defined PMMA chains grafted on the surface of CaCO₃/SiO₂ particles were only degraded by random chain scission of C C linkages within the PMMA chain, which is different from the degradation of PMMA chains prepared via traditional radical polymerization. This difference is reasonably ascribed to the difference between the end groups of PMMA prepared via reverse ATRP and that via traditional radical polymerization, which has been confirmed by end group analysis measured by ¹H–NMR spectroscopy.     

Synthesis of Poly (methyl methacrylate)/Zinc Oxide Nanocomposite with Core-Shell Morphology by Atom Transfer Radical Polymerization

A method to prepare zinc oxide (ZnO) nanoparticles with a covalently bonded poly(methyl methacrylate) (PMMA) shell by surface initiated atom transfer radical polymerization (ATRP) was reported. First, the initiator for ATRP was covalently bonded onto the surface of zinc oxide nanoparticles through our novel method. Firstly, the surface of ZnO nanoparticle was treated with 3-aminopropyl triethoxysilane, a silane coupling agent, and then this functionalization nanoparticle was reacted with α-chloro phenyl acetyl chloride to prepare atom transfer radical polymerization macroinitiator. The metal-catalyzed radical polymerization of MMA with ZnOmacroinitiator was performed using a copper catalyst system to give the ZnO-based nanoparticles hybrids linking PMMA segments (poly (methyl methacrylate)/zinc oxide nanocomposite). These hybrid nanoparticles had an exceptionally good dispersability in organic solvents and were subjected to detailed characterization using FTIR, TEM and TGA and DSC analyzed.     

Synthesis of well-defined, polymer-grafted silica nanoparticles via reverse ATRP

The surface grafting onto ultrafine silica via reverse ATRP of methyl methacrylate initiated by peroxide groups introduced onto the surface and conventional ATRP of Styrene initiated by the hybrid nanoparticles were investigated. The introduction of peroxide groups onto the silica surface was achieved by the reaction of hydrogen peroxide with chlorosilyl groups, which were introduced by the treatment of silica with thionyl chloride. Well-defined polymer chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined, densely grafted outer polymer layer. The polymerization was closely controlled in solution at quite low temperature such as 70 °C. In both cases, linear kinetic plots, linear plots of molecular weight (M_n) versus conversion, in hydrodynamic diameter with increasing conversion, and narrow molecular weight distributions (M_w/M_n) for the grafted polymer samples were observed. Hydrolysis of silica cores by hydrofluoric acid treatment enabled characterization of cleaved polymer using GPC. Ultrathin films of hybrid nanoparticles were examined using TEM and AFM.     

Preparation of well-defined polystyrene/silica hybrid nanoparticles by ATRP

Immobilization of the atom transfer radical polymerization (ATRP) macroinitiators at the silica nanoparticle surfaces was achieved through surface modification with excess toluene-2,4-diisocynate (TDI), after which the residual isocyanate groups were converted into ATRP macroinitiators. Structurally well-defined polystyrene chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined, densely grafted outer polystyrene by ATRP, which was initiated by the as-synthesized silica-based macroinitiator. FTIR, NMR and gel permeation chro-matography (GPC) were used to characterize the polystyrene/silica hybrid particles.     

Preparation of polymer‐grafted carbon black nanoparticles by surface‐initiated atom transfer radical polymerization

Pristine carbon black was oxidized with nitric acid to produce carboxyl group, and then the carboxyl group was consecutively treated with thionyl chloride and glycol to introduce hydroxyl group. The hydroxyl group on the carbon black surface was reacted with 2‐bromo‐2‐methylpropionyl bromide to anchor atom transfer radical polymerization (ATRP) initiator. The ATRP initiator on carbon black surface was verified by TGA, FTIR, EDS, and elemental analysis. Then, poly (methyl methacrylate) and polystyrene chains were respectively, grown from carbon black surface by surface‐initiated atom transfer radical polymerization (SI‐ATRP) using CuCl/2,2‐dipyridyl (bpy) as the catalyst/ligand combination at 110 °C in anisole. ¹H NMR, TGA, TEM, AFM, DSC, and DLS were used to systemically characterize the polymer‐grafted carbon black nanoparticles. Dispersion experiments showed that the grafted carbon black nanoparticles had good solubilities in organic solvents such as THF, chloroform, dichloromethane, DMF, etc. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3451–3459, 2007     

Organically capped silicon nanoparticles with blue photoluminescence prepared by hydrosilylation followed by oxidation

A facile method of preparing stable blue-emitting silicon nanoparticles that are dispersible in common organic solvents is presented. Oxidation of yellow-emitting silicon nanoparticles with an organic monolayer grafted to their surface, using either UV irradiation in solution or heating in air, converted them to blue-emitting particles. The evolution of the PL spectrum and infrared absorption spectrum of the particles was followed during the oxidation process. The PL spectrum showed a decrease in the PL emission peak near 600 nm and the appearance and increase in intensity of a PL emission peak near 460 nm rather than a smooth blue shift of the emission spectrum from yellow to blue. The organic monolayer grafted to the particle surface was not degraded by this oxidation process, as demonstrated by FTIR and NMR spectroscopy. Similar results were achieved for particles with styrene, 1-octene, 1-dodecene, and 1-octadecene grafted to their surface, demonstrating that it is the silicon nanocrystal, and not the organic component, that is essential to this process. The organic monolayer allows the nanoparticles to form stable, clear colloidal dispersions in organic solvents and provides for the possibility of further chemical functionalization of the particles. Combined with previous work on organically grafted silicon nanoparticles with green through near-infrared emission, this enables the efficient and scalable preparation of stable colloidal dispersions of organically grafted silicon nanoparticles with emission spanning the entire visible spectrum.     

Effects of incorporation of modified silica nanoparticles on the mechanical and thermal properties of PMMA

Silica nanoparticles of various sizes have been incorporated by melt compounding in a poly(methyl methacrylate) (PMMA) matrix to enhance its thermal and mechanical properties. In order to improve nanoparticles dispersion, PMMA grafted particles have been prepared by atom transfer radical polymerization (ATRP) from well-defined silica nanoparticles. This strategy was expected to ensure compatibility between both components of the PMMA nanocomposites. TEM analysis have been performed to evaluate the nanosilica dispersion whereas modified and non-modified silica/PMMA nanocomposites thermal stability and mechanical properties have been investigated by both thermogravimetric and dynamical mechanical analysis.     

Preparation of poly(methyl methacrylate) grafted hydroxyapatite nanoparticles via reverse ATRP

Surface-initiated reverse atom transfer radical polymerization (reverse ATRP) technical was successfully employed to modify hydroxyapatite (HAP) nanoparticles with poly(methyl methacrylate) (PMMA). The peroxide initiator moiety for reverse ATRP was covalently attached to the HAP surface through the surface hydroxyl groups. Reverse ATRP of methyl methacrylate (MMA) from the initiator-functionalized HAP was carried out, and the end bromide groups of grafted PMMA initiated ATRP of MMA subsequently. Fourier transformation infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and transmission electron microscopy (TEM) were employed to confirm the grafting and to characterize the nanoparticle structure. The grafted PMMA gave HAP nanoparticles excellent dispersibility in MMA monomer. As the amount of grafted PMMA increased, the dispersibility of surface-grafted HAP and the compressive strength of HAP/PMMA composites were improved.     

Thermosensitive copolymer networks modify gold nanoparticles for nanocomposite entrapment

The core-shell gold nanoparticles and copolymer of N-isopropylacrylamide (NIPAM) and N,N'-methylenebisacrylamide (MBAA) hybrids (Au@copolymer) were fabricated through surface-initiated atom-transfer radical polymerization (ATRP) on the surface of gold nanoparticles in 2-propanol/water mixed solvents. The surface of citrate-stabilized gold nanoparticles was first modified by a disulfide initiator for ATRP. The slight cross-linking polymerization between NIPAM and MBAA occurred on the gold surface and resulted in the formation of core-shell Au@copolymer nanostructures that were characterized by TEM, and FTIR and UV-visible spectroscopy. Such synthesized Au@copolymer hybrids possess clearly thermosensitive properties and exhibit "inspire" and "expire" water behavior in response to temperature changes in aqueous solution. Because of this property, we enable to trap and encapsulate smaller nanoparticles by using the free space of the copolymer-network scaffold anchored at the gold surface.     

Size, charge, and interactions with giant lipid vesicles of quantum dots coated with an amphiphilic macromolecule

Semiconductor colloidal quantum dots (QDs) are promising fluorescent probes for biology. Initially synthesized in organic solvents, they can be dispersed in aqueous solution by noncovalent coating with amphiphilic macromolecules, which renders the particles hydrophilic and modifies their interactions with other biological compounds. Here, after coating QDs with an alkyl-modified polyacrilic acid, we investigated their colloidal properties in aqueous buffers by electrophoresis, electron microscopy, light scattering, and rate zonal centrifugation. Despite polymer dispersity and variation of the size of the inorganic nanoparticles, the polymer-dot complexes appeared relatively well-defined in terms of hydrodynamic radius and surface charge. Our data show that these complexes contain isolated QD surrounded by a polymer layer with thickness 8-10 nm. We then analyzed their interaction with giant unilamellar vesicles, either neutral or cationic, by optical microscopy. At neutral pH, we found the absence of binding of the coated particles to lipid membrane, irrespective of their lipid composition. An abrupt surface aggregation of the nanoparticles on the lipid membrane was observed in a narrow pH range (6.0-6.2), indicative of critical binding triggered by polymer properties. The overall features of QDs coated with amphiphilic polymers open the route to using these nanoparticles in vivo as optically stable probes with switchable properties.     

PEG-POSS assisted facile preparation of amphiphilic gold nanoparticles and interface formation of Janus nanoparticles

A general approach to transfer water-soluble nanoparticles with different shapes, sizes, and surface charges into organic solvents, retaining their surface charge properties was developed, and its application in fabrication of hybrid Janus particles with opposite charges in solution was also demonstrated.     

Liquid-liquid phase-transfer of magnetic nanoparticles in organic solvents

We report a novel route for the preparation of well-defined colloidal dispersions of magnetic nanoparticles stabilized by steric repulsion in organic solvents. The usual methods standardly lead to the surfaction of multiparticle aggregates, incompatible with our long-term aim of studying and modeling the influence of magnetic dipolar interactions in colloidal dispersions which are free of aggregates, all other interactions being perfectly defined. A new and reproducible method based on a surfactant-mediated liquid-liquid phase transfer of individually dispersed gamma-Fe(2)O(3) nanoparticles from an aqueous colloidal dispersion to an organic phase is developed. The choice of the reagent and the preparation techniques is discussed. Among several solvent/surfactant pairs, the cyclohexane/dimethyldidodecylammonium bromide (DDAB) system is found to fulfill the colloidal stability criterion: aggregation does not appear, even upon aging. A complete transfer of isolated particles is observed above a threshold in DDAB concentration. The nanoparticle surface is then fully covered with adsorbed DDAB molecules, each surfactant head occupying a surface of 0.57+/-0.05 nm(2). The volume fraction of the cyclohexane-based organosols is easily tunable up to a volume fraction of 12% by modifying the volume ratio of the organic and of the aqueous phases during the liquid-liquid phase transfer.     

Effect of Solvents Treatment on Microstructure and Dispersion Properties of Palygorskite

Palygorskite was dispersed by various organic solvents and water, and the effects of solvent types on its microstructure, dispersion degree, and colloidal properties were investigated by infrared spectroscopy (IR), x-ray diffraction (XRD), and nitrogen adsorption-desorption isotherm (BET), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and rheological analyses. It was found that dimethyl sulfoxide and dimethyl formamide molecules may attach onto the surface of palygorskite and cause a complete disappearance of micropores. Solvent parameters govern the dispersion degree of palygorskite, and dimethyl sulfoxide and dimethyl formamide are good solvents to disperse palygorskite aggregates in contrast to ethanol and isopropanol. Colloidal stability and rheological tests suggested dimethyl sulfoxide-dispersed palygorskite can form more stable suspension with higher shear stress and modulus, but isopropanol-dispersed palygorskite may rapidly subside in suspension and show poor colloidal properties.     

油溶性Ag纳米微粒的制备及表征

Surface modified silver nano particles were synthesized in a mixture solvent of water-alcohol with Pyridinium di-n-octadecyldithio phosphate(PyDDP) as a modification agent. Themorphology and structure of DDP-coated Ag (Ag-DDP) nanoparticles were characterized using X-ray powder diffraction(XRD), Transmission electron microscopy(TEM), Fourier transform infrared spectrum (FT-IR) and Thermo gravimetric analysis(TGA). Anti wear properties of Ag-DDP nano particles were tested using a four-ball tribological testing machine. The disperse properties of Ag-DDP nanoparticles were evaluated in solvents such as chloroform, benzen, toluene, liquid paraffin, distilled water and ethanol. The results show that Ag-DDP nanoparticles disperse in organic solvents, but they don’t disperse in water or ethanol. The good disperse properties in organic solvents enable Ag-DDP nanoparticles to be used as oil additives. The XRD pattern of Ag-DDP nanoparticles indicates that they have fcc crystal structure, and the modification layer can prevent the oxidation of Ag nanocores. TEM graphs show that Ag-DDP nanoparticles have a homogeneous grain distribution; the average diameter is about 15nm. FT-IR and TGA curves indicate that the existence of modification layer can prevent the adsorption of water on the surface of nanoparticles. Tribological tests show that Ag-DDP nanoparticles have good anti-wear properties in liquid paraffin, and they can improve the applied load of base oil.     

Narrow-disperse Highly Cross-linked “Living” Polymer Microspheres by Two-stage Precipitation Polymerization

Narrow-disperse, surface-functionalized "living" polymer microspheres with uniformly cross-linked structures were prepared by two-stage precipitation copolymerization of styrene and divinylbenzene. The two-stage precipitation polymerization is composed of an initial conventional precipitation polymerization for the nucleation followed by a reverse atom transfer radical polymerization(reverse ATRP) for the controlled polymerization process. The polymerization parameters(including reaction time for the first stage, AIBN amount and monomer loading) have been studied to show significant influences on the morphologies. Moreover, narrower size distribution and an ATRP initiator-functional surface of resulting particles can be obtained by applying reverse ATRP to conventional precipitation polymerization in the second stage. Furthermore, the "livingness" of the resulting polymer microspheres was testified by their surface modification of poly[2-(dimethylamino) ethyl methacrylate](PDMAEMA) brushes via surface-initiated ATRP(SI-ATRP).     

Bifunctional nanoparticles with fluorescence and magnetism via surface-initiated AGET ATRP mediated by an iron catalyst

Fluorescent/magnetic nanoparticles are of interest in many applications in biotechnology and nanomedicine for its living detection. In this study, a novel method of surface modification of nanoparticles was first used to modify a fluorescent monomer on the surfaces of magnetic nanoparticles directly. This was achieved via iron(III)-mediated atom-transfer radical polymerization with activators generated by electron transfer (AGET ATRP). Fluorescent monomer 9-(4-vinylbenzyl)-9H-carbazole (VBK) was synthesized and was grafted from magnetic nanoparticles (ferroferric oxide) via AGET ATRP using FeCl(3)·6H(2)O as the catalyst, tris(3,6-dioxaheptyl)amine (TDA-1) as the ligand, and ascorbic acid (AsAc) as the reducing agent. The initiator for ATRP was modified on magnetic nanoparticles with the reported method: ligand exchange with 3-aminopropyltriethoxysilane (APTES) and then esterification with 2-bromoisobutyryl bromide. After polymerization, a well-defined nanocomposite (Fe(3)O(4)@PVBK) was yielded with a magnetic core and a fluorescent shell (PVBK). Subsequently, well-dispersed bifunctional nanoparticles (Fe(3)O(4)@PVBK-b-P(PEGMA)) in water were obtained via consecutive AGET ATRP of hydrophilic monomer poly(ethylene glycol) methyl ether methacrylate (PEGMA). The chemical composition of the magnetic nanoparticles' surface at different surface modification stages was investigated with Fourier transform infrared (FT-IR) spectra. The magnetic and fluorescent properties were validated with a vibrating sample magnetometer (VSM) and a fluorophotometer. The Fe(3)O(4)@PVBK-b-P(PEGMA) nanoparticles showed an effective imaging ability in enhancing the negative contrast in magnetic resonance imaging (MRI).     

Efficient surface grafting of luminescent silicon quantum dots by photoinitiated hydrosilylation

We suggest a method for efficient (high-coverage) grafting of organic molecules onto photoluminescent silicon nanoparticles. High coverage grafting was enabled by use of a modified etching process that produces a hydrogen-terminated surface on the nanoparticles with very little residual oxygen and by carefully excluding oxygen during the grafting process. It had not previously been possible to produce such a clean H-terminated surface on free silicon nanoparticles or, subsequently, to produce grafted particles without significant surface oxygen. This allowed us to (1) prepare air-stable green-emitting silicon nanoparticles, (2) prepare stable dispersions of grafted silicon nanoparticles in a variety of organic solvents from which particles can readily be precipitated by addition of nonsolvent, dried, and redispersed, (3) separate these nanoparticles by size (and therefore emission color) using conventional chromatographic methods, (4) protect the particles from chemical attack and photoluminescence quenching, and (5) provide functional groups on the particle surface for further derivatization. We also show, using 1H NMR, that the photoinitiated hydrosilylation reaction does not specifically graft the terminal carbon atom to the surface but that attachment at both the first and second atom occurs.     

CO2-expanded liquid deposition of ligand-stabilized nanoparticles as uniform, wide-area nanoparticle films

Deposition of nanoparticles into uniform, wide-area thin films using CO(2) as an antisolvent is presented. Ligand-stabilized silver particles are controllably precipitated from organic solvents by pressurizing and expanding the solution with carbon dioxide. Subsequent addition of carbon dioxide as a dense supercritical fluid provides for removal of the organic solvent while avoiding the surface tensions common to evaporating solvents that are detrimental to nanoscale assemblies and structures. This brand new CO(2)-expanded liquid particle deposition technique allows for the targeted deposition of particles and results in more uniform and lower defect metal nanoparticle thin films than are provided by conventional solvent evaporation techniques.     

Water-dispersible, uniform nanospheres by heating-enabled micellization of amphiphilic block copolymers in polar solvents

Uniform nanospheres with tunable size down to 30 nm were prepared simply by heating amphiphilic block copolymers in polar solvents. Unlike reverse micelles prepared in nonpolar, oily solvents, these nanospheres have a hydrophilic surface, giving them good dispersibility in water. Furthermore, they are present as individual, separated, rigid particles upon casting from the solution other than continuous thin films of merged micelles cast from micellar solution in nonpolar solvents. These nanospheres were generated by a heating-enabled micellization process in which the affinity between the solvent and the polymer chains as well as the segmental mobility of both hydrophilic and hydrophobic blocks was enhanced, triggering the micellization of the glassy copolymers in polar solvents. This heating-enabled micellization produces purely well-defined nanospheres without interference of other morphologies. The micelle sizes and corona thickness are tunable mainly by changing the lengths of the hydrophobic and hydrophilic blocks, respectively. The heating-enabled micellization route for the preparation of polymeric nanospheres is extremely simple, and is particularly advantageous in producing rigid, micellar nanospheres from block copolymers with long glassy, hydrophobic blocks which are otherwise difficult to prepare with high efficiency and purity. Furthermore, encapsulation of hydrophobic molecules (e.g., dyes) into micelle cores could be integrated into the heating-enabled micellization, leading to a simple and effective process for dye-labeled nanoparticles and drug carriers.