Preparation and characterization of temperature‐ and pH‐responsive diblock copolymers and their silica‐coated nanoparticles

Multiresponsive amphiphilic poly(N,N‐dimethylaminoethyl methacrylate)‐b‐poly(N‐isopropylacrylamide) (PDMAEMA‐b‐PNIPAM) was successfully synthesized by reversible addition‐fragmentation chain transfer polymerization. Poly(N,N‐dimethylaminoethyl methacrylate)‐b‐poly(N‐isopropylacrylamide) has thermal and pH stimuli responsiveness. Their lower critical solution temperature and hydrodynamic radius can be adjusted by varying the copolymer composition, block length, solution pH, and temperature. In addition, a convenient method has been established to prepare cross‐linked silica‐coated nanoparticles with PDMAEMA‐b‐PNIPAM micelles as a template, resulting in good organic/inorganic hybrid nanoparticles defined as 175 to 220 nm. The structure and morphology were characterized by proton nuclear magnetic resonance (₁HNMR), Fourier‐transform infrared spectroscopy (FT‐IR), transmission electron microscopy (TEM), and transmission electron microscopy‐energy dispersive X‐ray spectroscopy (TEM‐EDS).     

Preparation of Ag‐Embedded Polystyrene Nanospheres and Nanocapsules by Miniemulsion Polymerization

An isopropyl myristate (IPM) biocompatible oil and an IPM solution of dodecanethiol‐capped Ag nanoparticles (NPs, 4.5 nm) were used as hydrophobes to suppress the Ostwald ripening of monomer/hydrophobe miniemulsified droplets in a surfactant‐stabilized water phase. The formation of non‐IPM‐encapsulated nanospheres (48 nm) and IPM‐encapsulated nanocapsules (90 nm) were precisely controlled by using a water‐soluble and an oil‐soluble initiator, respectively, in the presence of a pure IPM as a hydrophobe in miniemulsion polymerization. Well‐defined PS nanospheres, on which surfaces were coated with Ag NPs (Ag/PS nanospheres, 65 nm), and nanocapsules encapsulating both NPs and IPM liquid phase (Ag‐IPM/PS nanocapsules, 115 nm) were made by replacing the hydrophobe from pure IPM with Ag/IPM solution. These nanostructures were characterized by transmission and scanning electron microscopes.

     

Preparation of glycopolymer‐substituted gold nanoparticles and their molecular recognition

Glycopolymer‐substituted gold nanoparticles were prepared via living radical polymerization with a reversible addition‐fragmentation chain transfer (RAFT) reagent. Polyacrylamide derivatives with α‐mannose (α‐Man) and N‐acetyl‐β‐glucosamine (β‐GlcNAc) were synthesized and hydrogenated to obtain thiol‐terminated polymer. The thiol‐terminated glycopolymers were mixed with gold nanoparticles to yield the polymer substituted gold nanoparticles with various diameters, which aggregated on addition of saccharide‐recognition proteins (lectins). The aggregation properties were analyzed using transmission electron microscopy and UV spectra. Molecular recognition was studied with E. coli, which induced aggregation of the nanoparticles at the cell periphery. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1412–1421, 2009     

Water‐soluble polymer‐grafted platinum nanoparticles for the subsequent binding of enzymes. synthesis and SANS

Functionalized platinum nanoparticles (PtNPs) possess catalytic properties towards H₂0₂ oxidation, which are of great interest for the elaboration of electrochemical biosensors. To improve the understanding of phenomena involved in such systems, we designed platinum‐polymer‐enzyme model nanostructures according to a bottom–up approach. These structures have been elaborated from elementary building units based on polymer‐grafted PtNPs obtained from surface initiated‐atom transfer radical polymerization. This paper describes the polymerization of ter‐butyl methacrylate from PtNPs and its subsequent hydrolysis to obtain a water‐soluble corona, followed by an activated ester modification to introduce an enzyme (glucose oxidase). The structure of the objects, the molecular weight and the grafting density of the polymer chains were principally elucidated by small angle neutron scattering (SANS). After the grafting of the enzyme, the final hybrid structures were characterized by both microscopy and SANS to attest for the covalent grafting of the enzyme. Composition and enzyme activity of the nanohybrid objects, have also been determined by UV spectroscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Preparation of monodispersed polystyrene microspheres uniformly coated by magnetite via heterogeneous polymerization

Composite microspheres of core-shell type were prepared by a seeded polymerization using monodispersed polystyrene seed latex (Ps) combined with an in situ dispersion of magnetite (Fe₃O₄) fine particles. The heterogeneous polymerization was carried out in aqueous dispersions of the Fe₃O₄ particles modified with sodium oleate. All the synthetic processes were carried out in a wet state to avoid serious agglomeration. The morphology of the composite particle and the size distribution were examined to discuss the effects on the polymerization parameters, such as monomer concentration, type and concentration of an initiator, magnetite particle concentration and the method of surface modification of Fe₃O₄.     

Pesticide‐conjugated polyacrylate nanoparticles: novel opportunities for improving the photostability of emamectin benzoate

Emamectin benzoate, a macrocyclic lactone, can be used in low quantities to control arthropod pests, effectively. However, its poor photostability prevents its further use. To delay its photodegradation, novel acrylate‐type polymeric nanoparticles were synthesized and tested as materials for improving pesticide photostability. N‐acylated emamectin benzoate was synthesized via bonding emamectin benzoate to acrylamide. The resulting pesticide, containing the double bond linkage –C=C–N–, was copolymerized with butyl acrylate and methyl methacrylate by the emulsion polymerization method. The refined polymers were characterized by Fourier transform infrared spectroscopy spectroscopy, and result illustrated the pesticide was conjugated to the polymers. Atomic force microscope and dynamic light scattering analyses were also used for determining the average particle diameters of pesticide–polymer conjugates. Photostability tests showed that the nanoparticles obtained exhibited greatly improved photostability. Additionally, the laboratory toxicity tests demonstrated that the insecticidal effects of the novel emamectin benzoate formulation were better than those of the control pesticide formulation (emamectin benzoate EC). Copyright © 2012 John Wiley & Sons, Ltd.     

Biocompatibility and hyperthermia cancer therapy of casein‐coated iron oxide nanoparticles in mice

Magnetic nanoparticles (MNPs) can be used as heat generation source in cancer hyperthermia therapy. While iron oxide nanoparticles (NPs) are the most popular choice for magnetic hyperthermia, adding a surface enhancement can improve its performance. Furthermore, for MNPs to be used in biomedical application their cytotoxicity needs to be evaluated. In this study biocompatibility and also in vivo performance of casein‐coated MNPs were assessed. Cell viability of normal cell lines in all of tests remained above 95% for 0.5 and 1 mg/mL concentration and even the minimum recorded cell viability for normal cell lines was 84.78% at 20 mg/mL concentration. In contrast cell viability of cancer cell lines in contact with casein coated MNPs core‐shell structure except for one sample remained below 85%. By introduction of and alternating magnetic field, cell viability of samples with lower MNP concentration dropped by 20% to 30% while this drop for samples with higher concentration was 10% to 20%. Furthermore, results of in vivo trials show that just 1 week of hyperthermia treatment with casein coated MNPs core‐shell structure can reduce the tumor size of the mice by 33%. Real‐time polymerase chain reaction results further confirmed the effectiveness of this method. Moreover, findings of this study suggest that lower injection speed can improve NPs distribution and treatment effect. Results of this study suggest that core‐shell structure can positively affect the tumor growth and the combination of good biocompatibility, innate hostility toward cancer cells and good heating power makes them a good candidate for hyperthermia cancer therapy applications.     

From single‐chain folding to polymer nanoparticles via intramolecular quadruple hydrogen‐bonding interaction

Single‐chain folding via intramolecular noncovalent interaction is regarded as a facile mimicry of biomacromolecules. Single‐chain folding and intramolecular crosslinking is also an effective method to prepare polymer nanoparticles. In this study, poly(methyl methacrylate‐co?2‐ureido‐5‐deazapterines functionalized ethylene methacrylate) (P(MMA‐co‐EMA‐DeAP)) is synthesized via free radical polymerization. The single‐chain folding of P(MMA‐co‐EMA‐DeAP) and the formation of the nanoparticles in diluted solution (concentration <0.005 mg/mL) are achieved via supramolecular interaction and intramolecular collapsing during the disruption‐reformation process of the hydrogen bonding triggered by water. The size and the morphology of the nanoparticles are characterized by dynamic light scattering, transmission electron microscope, and atomic force microscope. The results show that the size of the nanoparticles depends on the molecular weight of the polymer and the loading of 2‐ureido‐5‐deazapterines functionalized ethylene methacrylate (EMA‐DeAP) on the polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1832–1840     

Polyelectrolyte complex nanoparticles from chitosan and poly(acrylic acid) and Polystyrene‐block‐poly(acrylic acid)

Interpolymer polyelectrolyte complexes of chitosan (CS) with poly(acrylic acid) homopolymers and polystyrene‐block‐poly(acrylic acid) diblock copolymers were prepared and characterized. The influence of the positive/negative charge balance (charge ratio), pH, and ionic strength were thoroughly studied by dynamic light scattering. The existence of a strong polyelectrolyte effect was also highlighted in this study. Domains of stability, in which nanoparticle sizes are smaller than 100 and 200 nm for complexes of CS with the homopolymer and copolymer, respectively, were identified and confirmed by scanning electron microscopy and atomic force microscopy. The charged nature of the surface of the nanoparticles was evidenced by Zeta potential measurements. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polypyrrole‐coated alginate/magnetite nanoparticles composite sorbent for the extraction of endocrine‐disrupting compounds

Magnetite nanoparticles incorporated into alginate beads and coated with a polypyrrole adsorbent were prepared (polypyrrole/Fe₃O₄/alginate bead) and used as an effective magnetic solid‐phase extraction sorbent for the extraction and enrichment of endocrine‐disrupting compounds (estriol, β‐estradiol and bisphenol A) in water samples. The determination of the extracted endocrine‐disrupting compounds was performed using high‐performance liquid chromatography with a fluorescence detector. The effect of various parameters on the extraction efficiency of endocrine disrupting compounds were investigated and optimized including the type and amount of sorbent, sample pH, extraction time, stirring speed, and desorption conditions. Under optimum conditions, the calibration curves were linear in the concentration range of 0.5–100.0 μg/L, and the limit of detection was 0.5 μg/L. The developed method showed a high extraction efficiency, the recoveries were in the range of 90.5 ± 4.1 to 98.2 ± 5.5%. The developed sorbent was easy to prepare, was cost‐effective, robust, and provided a good reproducibility (RSDs < 5%), and could be reused 16 times. The developed method was successfully applied for the determination of endocrine‐disrupting compounds in water samples.     

Microwave‐assisted graft polymerization of ε‐caprolactone onto magnetite

The graft polymerization of ε‐caprolactone (ε‐CL) onto magnetite was carried out under microwave irradiation in the presence of tin(II) 2‐ethylhexanoate. The molar ratio of ε‐CL to tin(II) 2‐ethylhexanoate was 300, whereas the molar ratio of ε‐CL to magnetite was 5. The chemical structures of the obtained poly(ε‐caprolactone) coated magnetic nanoparticles were characterized by FTIR and XPS spectroscopy. These magnetic‐polymer hybrid nanostructures were further investigated by X‐ray diffraction and magnetization measurements. The morphology of the magnetic core‐shell nanostructures were determined by TEM. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5397–5404, 2009     

Polyelectrolyte complexes. VI. Polycation structure,polyanion molar mass,and polyion concentration effects on complex nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate)

The formation and characterization of some interpolyelectrolyte complex (IPEC) nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) (NaPAMPS), as a function of the polycation structure, polyanion molar mass, and polyion concentration, were followed in this work. Poly(diallyldimethylammonium chloride) and two polycations (PCs) containing (N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride) units in the backbone (PCA₅ and PCA₅D₁) were used as starting polyions. The complex stoichiometry, (n^?/n⁺)_iso, was pointed out by optical density at 500 nm (OD₅₀₀), polyelectrolyte titration, and dynamic light scattering. IPEC nanoparticle sizes were influenced by the polycation structure and polyanion molar mass only before the complex stoichiometry, which was higher for the more hydrophilic polycations (PCA₅ and PCA₅D₁) and for a higher NaPAMPS molar mass, and were almost independent of these factors after that, at a flow rate of the added polyion of about 0.28 mL × (mL PC)^?1 × h^?1. The IPEC nanoparticle sizes remained almost constant for more than 2 weeks, both before and after the complex stoichiometry, at low concentrations of polyions. NIPECs as stable colloidal dispersions with positive charges in excess were prepared at a ratio between charges (n^?/n⁺) of 0.7, and their storage colloidal stability, as a function of the polycation structure and polyion concentration (from 0.8 to ca. 7.8 mmol/L), was demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2495–2505, 2004     

An Oxygen‐Tolerant PET‐RAFT Polymerization for Screening Structure–Activity Relationships

The complexity of polymer–protein interactions makes rational design of the best polymer architecture for any given biointerface extremely challenging, and the high throughput synthesis and screening of polymers has emerged as an attractive alternative. A porphyrin‐catalysed photoinduced electron/energy transfer–reversible addition‐fragmentation chain‐transfer (PET‐RAFT) polymerisation was adapted to enable high throughput synthesis of complex polymer architectures in dimethyl sulfoxide (DMSO) on low‐volume well plates in the presence of air. The polymerisation system shows remarkable oxygen tolerance, and excellent control of functional 3‐ and 4‐arm star polymers. We then apply this method to investigate the effect of polymer structure on protein binding, in this case to the lectin concanavalin A (ConA). Such an approach could be applied to screen the structure–activity relationships for any number of polymer–protein interactions.     

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.     

Polyelectrolyte complexes. VII. Complex nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) tailored by the titrant addition rate

Nonstoichiometric interpolyelectrolyte complexes (IPECs) as colloidal dispersions have been widely used for the past decade as reactive materials for flocculation and surface modification. In this context, some new aspects of the preparation and properties of IPEC nanoparticles based on NaPAMPS, in salt‐free aqueous solutions, are reported in this article. IPEC dispersions with different characteristics, z‐averaged particle sizes, polydispersity indices, and colloidal stabilities were tailored by the addition rate of the titrant, a less investigated factor in the synthesis of IPECs as nanoparticles. Poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) (NaPAMPS) and two polycations bearing positive charges in the backbone, poly(diallyldimethylammonium chloride) and a polycation containing 95 mol % N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride units, were used for this purpose. The complex nanoparticle characteristics and storage stability were monitored via the optical density at 500 nm and dynamic light scattering. IPEC nanoparticles with z‐averaged particle sizes of 100–250 nm resulted from the same polyion pair and the same polyion concentrations when the addition rate of the titrant, either the polyanion or polycation, varied within the range of 0.1–1.5 mL/mL of the starting polyion × h. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5244–5252, 2004     

Polyester nanoparticles by non‐aqueous emulsion polycondensation

A versatile non‐aqueous emulsion polycondensation process for the mild fabrication of polyester nanoparticles is presented. Spherical nanoparticles with diameters smaller than 60 nm are prepared in non‐aqueous emulsion systems. These emulsions consisted in one case of DMF dispersed in n‐hexane and in a second with acetonitrile dispersed in a continuous cyclohexane phase. Stabilization of these systems was achieved by using a polyisoprene‐polymethylmethacrylate block copolymer. The suitability of these aprotic emulsions for synthesizing polyester nanoparticles by emulsion polycondensation having molecular weights up to 22,000 g/mol is demonstrated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1101–1108, 2007     

New polyelectrolytes based on 4‐vinyl‐1,2,3‐triazole and 1‐vinylimidazole

Copolymers of 4‐vinyl‐1,2,3‐triazole and 1‐vinylimidazole (VI) were obtained by radical copolymerization of (4‐vinyl‐1H‐1,2,3‐triazol‐1‐yl)methyl pivalate with VI followed by alkali hydrolysis. Reactivity ratios of the triazole and imidazole monomers are 0.51 and 0.30, respectively. Theoretical quantum‐chemical calculations by the PM3 semiempirical method give close values, which show that the obtained reactivity ratios reflect the activity of the vinyl groups. Polyelectrolyte properties of the copolymers were studied by potentiometric titration. Hydrogen bonds between the protonated triazole cycle and the triazole or imidazole units were found to considerably influence the solubility and solution properties of the copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Novel superhydrophobic silica/poly(siloxane‐fluoroacrylate) hybrid nanoparticles prepared via surface‐initiated ATRP and their surface properties: The effects of polymerization conditions

A series of superhydrophobic poly(methacryloxypropyltrimethoxysilane, MPTS‐b‐2,‐2,3,3,4,4,4‐heptafluorobutyl methacrylate, HFBMA)‐grafted silica hybrid nanoparticles (SiO₂/PMPTS‐b‐PHFBMA) were prepared by two‐step surface‐initiated atom transfer radical polymerization (SI‐ATRP). Under the adopted polymerization conditions in our previous work, the superhydrophobic property was found to depend on the SI‐ATRP conditions of HFBMA. As a series of work, in this present study, the effects of polymerization conditions, such as the initiator concentration, the molar ratio of monomer and initiator, and the polymerization temperature on the SI‐ATRP kinetics and the interrelation between the kinetics and the surface properties of the nanoparticles were investigated. The results showed that the SI‐ATRP of HFBMA was well controlled. The results also showed that both the surface microphase separation and roughness of the hybrid nanoparticles could be strengthened with the increase of the molecular weight of polymer‐grafted silica hybrid nanoparticles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Self‐assembly of a triblock terpolymer mediated by hydrogen‐bonded complexes

A poly(methyl methacrylate)‐block‐poly(4‐vinylpyridine)‐block‐polystyrene (PMMA‐b‐P4VP‐b‐PS) triblock terpolymer is synthesized by ATRP to study its self‐assembly with PAA in organic solvents. The self‐assembly behavior of this system is compared with the one of a mixture of two diblocks, namely polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) and poly(methyl methacrylate)‐block‐poly(methacrylic acid) (PMMA‐b‐PMAA). For both systems, formation of hydrogen‐bonded complexes between the P4VP and PMAA or PAA blocks occurs. These complexes become insoluble in the solvent used and micelles with a P4VP/P(M)AA complexes core surrounded by PS and PMMA coronal chains are obtained in both cases. These micelles are analyzed by DLS and TEM. Spherical micelles are formed for both systems but the hydrodynamic radii obtained for the two types of micelles are different. Indeed, the micelles formed by the PMMA‐b‐P4VP‐b‐PS + PAA system are smaller than those observed for the PS‐b‐P4VP + PMMA‐b‐PMAA system. Finally, the effect of the molar ratio of the P4VP/PMAA complexing blocks is investigated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 459–467     

Chitosan‐induced synthesis of magnetite nanoparticles via iron ions assembly

Superparamagnetic magnetite nanoparticles were synthesized induced by chitosan hydrogel under ambient conditions via iron ions assembly, and the inducing effect of chitosan hydrogel was discussed. Results of X‐ray diffraction and transmission electron microscopy indicate that the nanoparticles were inverse cubic spinel structure magnetite with diameter about 16 nm, and the superparamagnetic nanoparticles with narrow size distribution dispersed uniformly in chitosan. The magnetization measurements indicated that the nanoparticles showed the typical superparamagnetic behavior. The crystallinity, morphology, and magnetic properties of magnetite nanoparticles were remarkably influenced by the pH values of iron ion solutions. The interaction between magnetite and chitosan was illustrated by FT‐IR and thermogravimetric analysis, which concluded that the magnetite nanoparticles were coated by a chitosan layer via the amino groups of chitosan. The chitosan hydrogel assisted in the synthesis of superparamagnetic magnetite nanoparticles through chelation by amino groups. Copyright © 2008 John Wiley & Sons, Ltd.