Amine‐Reactive PEGylated Nanoparticles for Potential Bioconjugation

Water‐dispersible PEGylated nanoparticles (NPs) presenting amine‐reactive conjugation sites at their surfaces were synthesized and their ability to react with amines was demonstrated. An amphiphilic block copolymer bearing an N‐succinimidyl ester at its water‐soluble end was synthesized by the consecutive controlled radical polymerization of poly(ethylene glycol) methacrylate and styrene from a functional halide initiator. After purification of the copolymer, NPs of approximately 40 nm were obtained by a self‐assembly process in water. The reactivity of the NPs was evidenced by reacting them with primary amines, including a fluorescent dye. The activated ester remained stable throughout all synthetic steps and a nearly quantitative coupling efficiency was obtained.

     

Multifunctional Poly(2‐oxazoline) Nanoparticles for Biological Applications

New multifunctional copoly(2‐oxazoline) nanoparticles were prepared for cell studies. The polymer contains double‐bond side chains as potential reaction sites for “thio”‐click reactions as well as a fluorescein label covalently bound to the polymer backbone. Using the nanoprecipitation technique, spherical nanoparticles of 200–800 nm were obtained. Confocal laser scanning microscopy measurements revealed the cellular uptake of the nanoparticles.

     

Synthesis of Poly(methyl methacrylate) Nanoparticles Initiated by 2,2′‐Azoisobutyronitrile via Differential Microemulsion Polymerization

The synthesis of nanosized poly(methyl methacrylate) initiated by 2,2′‐azoisobutyronitrile via differential microemulsion polymerization has been investigated. Poly(methyl methacrylate) with a molecular weight of around 1 × 10⁶ and a particle size of about 20 nm was achieved under mild reaction conditions. A typical condition was that the surfactant amount required could be as low as 1/130 of the monomer amount in weight, and the surfactant/water ratio could be as low as 1/600, which is much less than the corresponding amounts reported in the literature. “Molecular bricks”, i.e., nanoparticles in which there are only one or two polymer chains, can be achieved using mild conditions by differential microemulsion polymerization, which may have potential applications for making molecular devices.

     

Production of PMMA Nanoparticles Loaded with Praziquantel Through “In Situ” Miniemulsion Polymerization

PZQ is the primary drug for treatment of schistosomiasis, but its efficiency is severely affected by its bitter taste. The main objective of this paper is the preparation of PMMA nanoparticles loaded with PZQ through in situ miniemulsion polymerizations and intended for oral formulations. Polymerizations are performed with an ultra turrax and a high‐pressure homogenizer. Obtained nanoparticles are analyzed by DSC, HPLC, DLS, GC, SEM, and PZQ dissolution profiles. Obtained results indicate the successful encapsulation of PZQ in all runs. Obtained data also show that the high‐pressure homogenizer leads to the best performance, allowing for preparation of stable latexes, with narrower particle size distributions and higher encapsulation efficiencies.

     

Synthesis and characterization of poly(methyl methacrylate)‐block‐poly(methylphenylsilane)‐ block‐poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with ¹H NMR and ¹³C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003     

Luminescent polymeric ruthenium complexes with polystyrene‐b‐poly(methyl methacrylate) macroligands: The sequential activation of initiator sites for blocks generated by parallel polymerization mechanisms

The synthesis of polystyrene‐b‐poly(methyl methacrylate) diblock copolymers with a luminescent ruthenium(II) tris(bipyridine) [Ru(bpy)₃] complex at the block junction is described. The macroligand precursor, polystyrene bipyridine‐poly(methyl methacrylate) [bpy(PS–H)(PMMA)], was synthesized via the atom transfer radical polymerization of styrene and methyl methacrylate from two independent, sequentially activated initiating sites. Both polymerization steps resulted in the growth of blocks with sizes consistent with monomer loading and narrow molecular weight distributions (i.e., polydispersity index < 1.3). Subsequent reactions with ruthenium(II) bis(bipyridine) dichloride [Ru(bpy)₂Cl₂] in the presence of Ag⁺ generated the ruthenium tris(bipyridine)‐centered diblock, which is of interest for the imaging of block copolymer microstructures and for incorporation into new photonic materials. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4250–4255, 2002     

Compatibilizing effect of a graft copolymer on bacterial poly(3‐hydroxybutyrate)/poly(methyl methacrylate) blends

Blends of isotactic (natural) poly(3‐hydroxybutyrate) (PHB) and poly(methyl methacrylate) (PMMA) are partially miscible, and PHB in excess of 20 wt % segregates as a partially crystalline pure phase. Copolymers containing atactic PHB chains grafted onto a PMMA backbone are used to compatibilize phase‐separated PHB/PMMA blends. Two poly(methyl methacrylate‐g‐hydroxybutyrate) [P(MMA‐g‐HB)] copolymers with different grafting densities and the same length of the grafted chain have been investigated. The copolymer with higher grafting density, containing 67 mol % hydroxybutyrate units, has a beneficial effect on the mechanical properties of PHB/PMMA blends with 30–50% PHB content, which show a remarkable increase in ductility. The main effect of copolymer addition is the inhibition of PHB crystallization. No compatibilizing effect on PHB/PMMA blends with PHB contents higher than 50% is observed with various amounts of P(MMA‐g‐HB) copolymer. In these blends, the graft copolymer is not able to prevent PHB crystallization, and the ternary PHB/PMMA/P(MMA‐g‐HB) blends remain crystalline and brittle. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1390–1399, 2002     

Rheological,mechanical and morphological properties of thermoplastic vulcanizates based on NR‐g‐PMMA/PMMA blends

Graft copolymer of natural rubber and poly(methyl methacrylate) (NR‐g‐PMMA) was prepared using semi‐batch emulsion polymerization technique via bipolar redox initiation system. It was found that the grafted PMMA increased with the increase of methyl methacrylate (MMA) concentration used in the graft copolymerization. The NR‐g‐PMMA was later used to prepare thermoplastic vulcanizates (TPVs) by blending with PMMA through dynamic vulcanization technique. Conventional vulcanization (CV) and efficient sulphur vulcanization (EV) systems were studied. It was found that the CV system provided polymer melt with lower shear stress and viscosity at a given shear rate. This causes ease of processability of the TPVs via extrusion and injection molding processes. Furthermore, the TPVs with the CV system showed higher ultimate tensile strength and elongation. The results correspond to the morphological properties of the TPVs. That is, finer dispersion of the small vulcanized rubber particles were observed in the PMMA matrix. Various blend ratios of the NR‐g‐PMMA/PMMA blends using various types of NR‐g‐PMMA (i.e. prepared using various percentage molar ratios of NR and MMA) were later studied via dynamic vulcanization by a conventional sulphur vulcanization system. It was found that increasing the level of PMMA caused increasing trend of the tensile strength and hardness properties but decreasing level of elongation properties. Increasing level of the grafted PMMA in NR molecules showed the same trend of mechanical properties as in the case of increasing concentration of PMMA used as a blend component. From morphological studies, two phase morphologies were observed with a continuous PMMA phase and dispersed elastomeric phase. It was also found that more finely dispersed elastomeric phase was obtained with increasing the grafted PMMA in the NR molecules. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and characterization of amphiphilic triblock copolymers by iron‐mediated atom transfer radical polymerization

The atom transfer radical polymerization of methyl methacrylate (MMA) and n‐butyl methacrylate (n‐BMA) was initiated by a poly(ethylene oxide) chloro telechelic macroinitiator synthesized by esterification of poly(ethylene oxide) (PEO) with 2‐chloro propionyl chloride. The polymerization, carried out in bulk at 90 °C and catalyzed by iron(II) chloride tetrahydrate in the presence of triphenylphosphine ligand (FeCl₂ · 4H₂O/PPh₃), led to A–B–A amphiphilic triblock copolymers with MMA or n‐BMA as the A block and PEO as the B block. A kinetic study showed that the polymerization was first‐order with respect to the monomer concentration. Moreover, the experimental molecular weights of the block copolymers increased linearly with the monomer conversion, and the molecular weight distribution was acceptably narrow at the end of the reaction. These block copolymers turned out to be water‐soluble through the adjustment of the content of PEO blocks (PEO content >90% by mass). When the PEO content was small [monomer/macroinitiator molar ratio (M/I) = 300], the block copolymers were water‐insoluble and showed only one glass‐transition temperature. With an increase in the concentration of PEO (M/I = 100 or 50) in the copolymer, two glass transitions were detected, indicating phase separation. The macroinitiator and the corresponding triblock copolymers were characterized with Fourier transform infrared, proton nuclear magnetic resonance, size exclusion chromatography analysis, dynamic mechanical analysis, and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5049–5061, 2005     

Grafting Efficiency of Hydroxy‐Terminated Poly(methyl methacrylate) with Multiwalled Carbon Nanotubes

Summary: Poly(methyl methacrylate)s (PMMAs) containing a terminal hydroxy group or multiple hydroxy groups as pendants were grafted to multiwalled carbon nanotubes (MWNTs) by esterification in toluene at 100 °C. The recovered polymer with a low level of MWNTs and the PMMA‐g‐MWNTs with up to 12 wt.‐% grafted polymer were characterized using spectroscopic, microscopic, and thermogravimetric analyses. The percentage of polymer present in the PMMA‐g‐MWNT samples is very low based upon the concentration of the acid groups in the tubes.

The grafting of hydroxy‐terminated PMMA to MWNTs by esterification.     

Catenated PS–PMMA Block Copolymers via Supramolecularly Templated ATRP Initiator Approach

A novel route to synthesize catenated macrocyclic PS–PMMA block copolymers is demonstrated via combination of supramolecular chemistry and controlled radical polymerization (CRP). Polymerization of styrene with bromopropionate ester initiator coupled with phenanthroline Cu(I) complex affords a four arm PS macroinitiator, which upon further chain extension by polymerization of MMA generates a four arm PS–PMMA block copolymer. Intramolecular coupling of PS–PMMA–Br arms via low temperature styrene‐assisted atom transfer radical coupling (ATRC) leads to the formation of PS–PMMA catenand, which generates the metal‐free catenated macrocyclic PS–PMMA block copolymer after removal of Cu metal. The interlocked structures of catenated block copolymers are confirmed by GPC, NMR, and AFM image analysis.     

Synthesis and Characterization of Dendrimer‐Encapsulated Bimetallic Core‐Shell PdPt Nanoparticles

Using a successive method, PAMAM dendrimer‐encapsulated bimetallic PdPt nanoparticles have been successfully prepared with core‐shell structures (Pd@Pt DENs). Evidenced by UV‐vis spectra, high resolution transmission electron microscopy, and X‐ray energy dispersive spectroscopy (EDS), the obtained Pd@Pt DENs are monodispersed and located inside the cavity of dendrimers, and they show a different structure from monometallic Pt or Pd and alloy PdPt DENs. The core‐shell structure of Pd@Pt DENs is further confirmed by infrared measurements with carbon monoxide (IR‐CO) probe. In order to prepare Pd@Pt DENs, a required Pd/Pt ratio of 1:2 is determined for the Pt shell to cover the Pd core completely. Finally, a mechanism for the formation of Pd@Pt DENs is proposed.     

One‐step synthesis of hyperbranched polyethylene macroinitiator and its block copolymers with methyl methacrylate or styrene via ATRP

Block copolymers of hyperbranched polyethylene (PE) and linear polystyrene (PS) or poly(methyl methacrylate) (PMMA) were synthesized via atom transfer radical polymerization (ATRP) with hyperbranched PE macroinitiators. The PE macroinitiators were synthesized through a “living” polymerization of ethylene catalyzed with a Pd‐diimine catalyst and end‐capped with 4‐chloromethyl styrene as a chain quenching agent in one step. The macroinitiator and block copolymer samples were characterized by gel permeation chromatography, ¹H and ¹³C NMR, and differential scanning calorimetry. The hyperbranched PE chains had narrow molecular weight distribution and contained a single terminal benzyl chloride per chain. Both hyperbranched PE and linear PS or PMMA blocks had well‐controlled molecular weights. Slow initiation was observed in ATRP because of steric effect of hyperbranched structures, resulting in slightly broad polydispersity index in the block copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3024–3032, 2010     

Block copolymers of styrene and n‐alkyl methacrylates with long alkyl groups. Micellization behavior in selective solvents

The micellization properties of well‐defined block copolymers of styrene and decyl methacrylate (SDMA) were studied in two different solvents, methyl acetate (MAc) selective for the polystyrene (PS) block and dodecane, selective for the poly(decyl methacrylate) (PDMA) block. The results were compared with those obtained, in the same solvents, from block copolymers of styrene and stearyl methacrylate (SSMA). In MAc, SDMA copolymers with a decyl methacrylate (DMA) content of 15% or less formed unimolecular micelles, whereas those with a content of 18.5% or higher formed multimolecular micelles. The degrees of association were lower than the corresponding SSMA samples. In dodecane, SDMA form large, monodisperse, spherical, and thermally stable micelles with degrees of association higher than the corresponding SSMA samples. The different behaviors can be attributed to the steric hindrance effect and the ability of the long alkyl groups of the polymethacrylate, MA blocks to crystallize. When the MA blocks are in the soluble corona of the micelles, the steric hindrance effect prevails, thus leading to higher degrees of association for the less bulky alkyl group. In the case where the MA block is in the insoluble core of the micelles, the higher the tendency for crystallization the higher the degree of association. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4177–4188, 2004     

Homo‐ and copolymerization of methyl methacrylate with ethylene by novel Ziegler‐Natta‐Type nickel catalysts based on N,O‐nitro‐substituted chelate ligands

New Nickel (II) catalytic systems based on N,O chelate ligands, activated by methylaluminoxane, have been checked in the homopolymerization of methyl methacrylate (MMA) and its copolymerization with ethylene. In particular, the bis(8‐hydroxy‐5‐nitro‐quinolate)nickel(II)/methylaluminoxane system as well as the catalysts obtained by oxidative addition of either 8‐hydroxy‐5‐nitro‐quinoline or 8‐hydroxy‐5,7‐dinitro‐quinoline or 4‐nitro‐2‐(p‐nitrobenzylideneamino)‐phenol to Ni(cod)₂, subsequently activated by methylaluminoxane, have been employed. The influence of the reaction parameters on the catalytic activity and the characteristics of the resulting polymers has been investigated. All the obtained poly(methyl methacrylate) samples display a largely prevailing syndiotacticity degree, high molecular weights and a rather large polydispersity. The catalytic systems obtained through the oxidative procedure are able also to give copolymers of MMA with ethylene producing highly linear polyethylenes containing a low amount (1.5–2 mol %) of MMA counits, thus affording materials with improved surface properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 620–633, 2006     

UV‐Free Microfluidic Particle Fabrication at Low Temperature Using ARGET‐ATRP as the Initiator System

A new way to fabricate monodisperse polymer particles in a microfluidic device without UV‐light and without the need for high temperatures is described in this article. By applying an activator regeneration by electron transfer ‐ atom transfer radical polymerization (ARGET‐ATRP) initiator system in a co‐capillary microfluidic setup and by separating the monomer mixture in an initiator and a catalyst phase, a fast polymerization of the droplets at low temperature without premature curing and thus clogging of the capillaries can be achieved. The influence of the flow rates on the particle sizes and their polydispersity as well as the controlled character of the polymerization are investigated. The particle size is well adjustable, but the reaction is not controlled due to the high radical concentration needed for rapid polymerization. In addition, particles with incorporated UV‐dyes are produced as a proof of concept at low temperature.

     

Preparation,Cellular Internalization,and Biocompatibility of Highly Fluorescent PMMA Nanoparticles

Methacrylate monomers were functionalized with a 4‐hydroxythiazole chromophore and copolymerized with methyl methacrylate via RAFT. Nanoparticles of 120 and 500 nm in size were prepared without using stabilizers/surfactants. For comparative studies, preparative ultracentrifugation was applied for the separation into small and large particle fractions. All suspensions were characterized by DLS, AUC, and SEM and tested regarding their stability during centrifugation and re‐suspension, autoclavation, and incubation in cell culture media. In vitro studies with mouse fibroblast cell line and differently sized NP showed a particle uptake into cells. Biocompatibility, non‐toxicity, and hemocompatibility were demonstrated using a XTT assay, a live/dead staining, and an erythrocyte aggregation and hemolysis assay.     

One‐Pot Synthesis of Multifunctional Polymers by Light‐Controlled Radical Polymerization and Enzymatic Catalysis with Candida antarctica Lipase B

The preparation of multifunctional polymers and block copolymers by a straightforward one‐pot reaction process that combines enzymatic transacylation with light‐controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light‐controlled polymerization, leading to multifunctional methacrylate‐based polymers with well‐defined microstructure.

     

Effect of Surface‐Hydroxylated CdS Nanoparticles on the Morphological Transformation of Polystyrene‐block‐Poly(ethylene oxide) Thin Films

Summary: Polystyrene‐block‐poly(ethylene oxide) (SEO) block copolymer thin films, in which CdS clusters have been sequestered into the PEO domains of the SEO block copolymers, are found to induce the morphological transformation of PEO from cylinders to spheres, as shown by using atomic force microscopy (AFM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). This transformation is caused by the presence of hydrogen‐bonding interactions between surface‐hydroxylated CdS and PEO, as confirmed by nuclear magnetic resonance (NMR) studies.

Morphological transformation of PEO cylinders into CdS/PEO spheres by hydrogen‐bonding interactions between surface‐hydroxylated CdS and PEO.