Characteristics of polypyrrole electrodeposited onto roughened substrates composed of gold–silver bimetallic nanoparticles

In this work, the characteristics of polypyrrole (PPy) films electrodeposited onto an electrochemically roughened gold substrate with bimetallic silver and gold nanoparticles were first investigated. First, a silver substrate was roughened by a triangular‐wave oxidation–reduction cycle (ORC) in an aqueous solution containing 0.1 M HCl. Subsequently, a gold substrate was roughened by a similar ORC treatment in this used solution. The results revealed that the surface of the roughened gold substrate demonstrated two different kinds of deposition domains because of the modification of silver nanoparticles. Encouragingly, some novel characteristics of PPy deposited onto this substrate were observed, in comparison with those on the roughened gold substrate without the modification of silver nanoparticles. They included a denser and more compact surface morphology, higher oxidation degree, increased conductivity, and improved surface‐enhanced Raman scattering. Furthermore, the nucleation and growth mechanism for PPy electropolymerization on this silver‐modified roughened gold substrate was distinguishable from that on the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2724–2731, 2006     

Effect of the polymer matrix on the formation of silver nanoparticles in polymer–silver salt complex membranes

When polymer–silver salt complex membranes were exposed to UV irradiation, the separation performances of both the permeance and selectivity for propylene–propane decreased, which was primarily attributed to the reduction of the silver ions in the membranes to silver nanoparticles. Here, the effect of the polymer matrix on the formation of silver nanoparticles in the polymer–silver salt complex membranes was investigated. This effect was assessed for the complexes of two kinds of silver salts (AgBF₄ and AgCF₃SO₃) with several polymeric ligands containing three different carbonyl groups, including poly(vinyl pyrrolidone) (PVP) with an amide group, poly(vinyl methyl ketone) (PVMK) with a ketone group, and poly(methyl methacrylate) (PMMA) with an ester group. UV–vis spectra and transmission electron microscopy (TEM) images clearly indicated that the reduction rate of the silver ions has the following order in the various polymer matrices: PVP > PVMK > PMMA, whereas the size and the distribution of the nanoparticles exhibited the reverse order. The tendency to form silver nanoparticles was explained in terms of the differences between the comparative strengths of the interactions of the silver ions with the different carbonyl oxygens in the matrices, as well as that of the silver ions with counteranions, which was characterized by X‐ray photoelectron spectroscopy (XPS) and FT‐Raman spectroscopy. It was concluded that when the concentration of free silver ions was low due to weak polymer–silver ion and strong silver ion–anion interactions, as found with PMMA, the reduction rate of silver ions to silver nanoparticles was slow. Therefore, the PMMA–silver complex membranes were less sensitive to decreases in separation performance upon UV irradiation than compared to the PVP membranes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1168–1178, 2006     

Tailored composite polymer–metal nanoparticles by miniemulsion polymerization and thiol‐ene functionalization

A simple and modular synthetic approach, based on miniemulsion polymerization, has been developed for the fabrication of composite polymer–metal nanoparticle materials. The procedure produces well‐defined composite structures consisting of gold, silver, or MnFe₂O₄ nanoparticles (～10 nm in diameter) encapsulated within larger spherical nanoparticles of poly(divinylbenzene) (～100 nm in diameter). This methodology readily permits the incorporation of multiple metal domains into a single polymeric particle, while still preserving the useful optical and magnetic properties of the metal nanoparticles. The morphology of the composite particles is retained upon increasing the inorganic content and also upon redispersion in organic solvents. Finally, the ability to tailor the surface chemistry of the composite nanoparticles and incorporate steric stabilizing groups using simple thiol‐ene chemistry is demonstrated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1594–1606, 2010     

Synthesis of P(AA‐SA)/ZnO composite latex particles via inverse miniemulsion polymerization and its application in pH regulation and UV shielding

Poly(acrylic acid‐co‐sodium acrylate)/zinc oxide, P(AA‐SA)/ZnO, composite latex particles were synthesized by inverse miniemulsion polymerization. The ZnO nanoparticles were prepared by hydrothermal synthesis and undergone oleic acid (OA) surface treatment. The X‐ray diffraction pattern and FT‐IR spectra characterized the crystal structure and functional groups of OA‐ZnO nanoparticles. An appropriate formulation in preparing P(AA‐SA) latex particles, ensuring the dominant in situ particle nucleation and growth, was developed in our experiment first. Sodium hydroxide was chosen as a costabilizer, because of its ability to increase the deprotonation of acylic acid and enhance the hydrophilicity of monomer, acrylic acid besides providing osmotic pressure. The growth mechanism of P(AA‐SA)/ZnO composite particles was proposed. The OA‐ZnO nanoparticles were adsorbed on or around the surface of P(AA‐SA) latex particles by hydrophobic interaction, thus enhanced the interfacial tension over latex particles. The P(AA‐SA)/ZnO composite latex particles owned better thermal stability than pure latex particles. The pH regulation capacity was excellent for both ZnO and P(AA‐SA) particles. Combining P(AA‐SA) and ZnO nanoparticles into composite particles, the performance in pH regulation and UV shielding was discussed from our experimental results. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8081–8090, 2008     

Simultaneous synthesis of silver nanoparticles and poly(2,5‐dimethoxyaniline) in poly(styrene sulfonic acid)

Silver nanoparticles were formed in situ along with poly(2,5‐dimethoxyaniline) (PDMA) in an interconnected network matrix (reactor), comprising the electronic conductive polymer, PDMA, and a polyelectrolyte, poly(styrene sulfonic acid) (PSS), through the simultaneous reduction of Ag⁺ ions and polymerization of 2,5‐dimethoxyaniline. In situ ultraviolet‐visible spectroscopy showed that peaks corresponding to the plasmon resonance of silver nanoparticles at 411 nm and the polaronic transition of PDMA at 438 nm provided evidences for the simultaneous formation of silver nanoparticles and PDMA. Transmission electron microscopy and size distribution analysis revealed the presence of spherical silver nanoparticles with an average diameter of 12 nm in the composite. X‐ray photoelectron spectroscopy showed that the amine units in PDMA changed to imine units upon the formation of silver nanoparticles. A comprehensive mechanism for the formation of the PDMA‐PSS‐Ag nanocomposite is proposed. A 10‐fold increase in the conductivity was noticed for the PDMA–PSS–Ag nanocomposite (1 S/cm) in comparison with the PDMA–PSS composite (0.1 S/cm). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3843–3852, 2006     

Metal nanocomposite films prepared in situ from PVA and silver nitrate. Study of the nanostructuration process and morphology as a function of the in situ routes

Cast‐hybrid films composed of polyvinyl alcohol (PVA) and silver nitrate were treated according to three different ways, thermal annealing, UV‐irradiation, and chemical reduction by a borohydride solution, to obtain PVA/silver nanocomposite films. The nanostructuration process was studied as a function of the treatment conditions, and discussed as a function of the mobility state of the polymer chains in the nanocomposite matrix during treatment. A homogeneous dispersion of crystalline silver nanoparticles was obtained by thermal annealing above T_g and below T_m and UV‐lamp irradiation below T_g. For these two treatments, the major processing parameters were the annealing temperature and time and the UV‐exposure time, respectively. For low‐conversion rate in Ag(0), the films evolved upon ageing at room temperature. Totally different morphology and Ag(0) conversion were achieved by chemical reduction in a borohydride solution. All the silver ions were reduced into Ag(0), and crystalline silver nanoparticles layers parallel to the film surface were observed after the treatment. This morphology was related to the high‐swollen state of the polymer matrix during treatment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2062–2071, 2008     

Exploring rheological properties of aqueous polyaniline‐PVP dispersion

Stable aqueous dispersion of polyaniline (PAn) stabilized by a hydrophilic polymer poly(vinyl pyrrolidone) (PVP) exhibits interesting rheological properties different from its components. Shear thinning observed for both PVP and PAn–PVP colloid (PP) indicates partially entangled nature of the later. Linear viscoelastic response of PVP solution exhibit strong frequency dependence of elastic (G′) and viscous (G″) modulus over the whole frequency range (0.1–100 ras/s) where G′ never exceeds G″ indicating the applicability of the Rouse‐Zimm model to this system. On the other hand, there is a crossover of G′ and G″ in the rheological profile of PP dispersion so that a single relaxation time model can be applicable. Therefore, PVP presents an entangled polymeric system and supposed to have a spectrum of relaxation times, whereas PP resembles to a physically crosslinked system with a single relaxation time. Increasing the extent of hydrogen bonding within the system (by raising the fraction of PAn or by leaving the solution undisturbed for long) relaxation time also becomes longer. The large difference in values of steady and complex shear viscosity (η and η*) within LVE regime reflects that original Cox‐Merz rule is obviously inapplicable to these systems. But at larger strain amplitude, η and η* are satisfactorily coincident that indicates a broader applicability of the modified Cox‐Merz rule. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2443–2455, 2008     

Preparation and characterization of monodisperse superparamagnetic poly(vinyl alcohol) beads by reverse spray suspension crosslinking

A novel protocol for preparing magnetic poly(vinyl alcohol) (PVA) beads by reverse spray suspension crosslinking was reported. The hydrophilic Fe₃O₄ nanoparticles were mixed with PVA, glutaraldehyde, and water to form aqueous phase. Then the aqueous phase was sprayed into vegetable oil by a pressure of nitrogen gas to form water in oil (W/O) suspension. The magnetic PVA beads were obtained in the presence of hydrochloric acid catalyst. It was found that the magnetic PVA beads obtained good properties when the PVA concentration was 10%, and the oil phase temperature was controlled at 40 °C. The mechanical stirring has little impact on the size of magnetic PVA beads in the process of reverse spray suspension crosslinking. The Cibacron Blue (CB) was coupled on the surface of magnetic PVA beads by surface chemical reaction. The morphology, size, and magnetic properties of the magnetic PVA beads were examined by scanning electron microscopy, laser diffraction, and vibrating sample magnetometer, respectively. Compared with the stirring method, it was found that the size of magnetic PVA beads was monodisperse and their saturation magnetization was much higher. Fourier transform infrared and X‐ray photoelectron spectroscopy experimental results proved that CB molecules were covalently immobilized onto the surface of the magnetic PVA beads. Meanwhile, the protein affinity separation experiments demonstrated that the magnetic PVA beads can potentially be used as a carrier for large‐scale protein separation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 203–210, 2008     

Photoinitiated dispersion polymerization of methyl methacrylate: A quick approach to prepare polymer microspheres with narrow size distribution

Photoinitiated dispersion polymerization of methyl methacrylate was carried out in a mixture of ethanol and water as dispersion medium in the presence of poly(N‐vinylpyrrolidone) (PVP) as the steric stabilizer and Darocur 1173 as photoinitiator. 93.7% of conversion was achieved within 30 min of UV irradiation at room temperature, and microspheres with 0.94 μm number–average diameter and 1.04 polydispersity index (PDI) were obtained. X‐ray photoelectron spectroscope (XPS) analysis revealed that only parts of surface of the microspheres were covered by PVP. The particle size decreased from 2.34 to 0.98 μm as the concentration of PVP stabilizer increased from 2 to 15%. Extra stabilizer (higher than 15%) has no effect on the particle size and distribution. Increasing medium polarity or decreasing monomer and photoinitiator concentration resulted in a decrease in the particle size. Solvency of reaction medium toward stabilizer, which affects the adsorption of stabilizer on the particle surface, was shown to be crucial for controlling particle size and uniformity because of the high reaction rate in photoinitiated dispersion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1329–1338, 2008     

Novel silver/polyurethane nanocomposite by in situ reduction: Effects of the silver nanoparticles on phase and viscoelastic behavior

A novel silver/poly(carbonate urethane) nanocomposite was prepared through in situ reduction of a silver salt (AgNO₃) added to a solution consisting of a commercial poly(carbonate urethane) dissolved in N,N‐dimethylformamide (DMF). In this system, the presence of the poly(carbonate urethane) was proved to protect the silver nanoparticles, whose formation was confirmed by means of UV–vis spectroscopy, from aggregation phenomena. The silver morphology developed in the solid state after DMF casting was imaged by FESEM. Homogeneous dispersion of silver nanoprisms in the poly(carbonate urethane) matrix was clearly observed. The effects of dispersion of silver nanoparticles within the poly(carbonate urethane) matrix were investigated by means of ATR‐FTIR and multifrequency dynamic mechanical thermal analyses. The obtained results revealed that the presence of silver nanoparticles modifies both the phase and the viscoelastic behaviors of poly(carbonate urethane). As a matter of fact, the hydrogen bond formation in the hard and soft segments was found to be hindered and the molecular motions of the soft segments were restricted, because a comparatively higher activation energy was required for the related α‐relaxation process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 344–350, 2008     

Functionalization and molecular dynamics study of carboxy‐terminated poly(1‐vinylpyrrolidin‐2‐one): A potential soluble carrier of biomolecules

The reactivity of carboxy‐terminated poly(1‐vinylpyrrolidin‐2‐one) (PVP‐COOH) 40‐mers 1 with various small bi‐functionalized molecules has been investigated. A number of new differently functionalized PVP 3–11 have been successfully obtained demonstrating that the presence of the bulky PVP chain did not hamper the reactivity of the carboxy group. This would imply that in solution the carboxyl group is not buried inside the coil, but well exposed to the solvent, as further confirmed by a molecular dynamics conformational study. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1683–1698, 2008     

Generation of radical species on polypropylene by alkylborane‐oxygen system and its application to graft polymerization

Graft polymerization of ethyl acrylate and n‐butyl acrylate onto surface of polypropylene (PP) beads (diameter: 3.2 mm) were carried out by using a redox system composed of triethylborane (Et₃B) and molecular oxygen in air. The amounts of the grafted polymers increased by prolonging a period of soaking PP beads in a solution of Et₃B in hexane, a less polar solvent of which affinity with PP would be higher than that of tetrahydrofuran, a highly polar solvent. These results implied that the present graft polymerization involved: (1) interpenetration of Et₃B into the surface area with the aid of hexane as a solvent, (2) its aerobic oxidation to generate a radical species, (3) abstraction of proton from PP by the radical species, and (4) initiation of polymerization from the resulting radical on the PP surface. Besides the acrylates, acrylic acid, and glycidyl methacrylate were also grafted onto the surface of PP to endow it with carboxyl and epoxy moieties, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6163–6167, 2009     

Emulsion synthesis of nanoparticles containing PEDOT using conducting polymeric surfactant: Synergy for colloid stability and intercalation doping

Poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is a widely used conductive aqueous dispersion synthesized by using emulsion polymerization method. To further enhance its solution processability and conductivity of PEDOT derivatives, we proposed to replace the nonconductive PSS with conductive poly[2‐(3thienyl)‐ethoxy‐4‐butylsulfonate] (PTEB) as surfactant for the emulsion polymerization of PEDOT. The reaction involved colloid stabilization and doping in one step, and yielded PEDOT:PTEB composite nanoparticles with high electrical conductivity. Contrary to its counterpart containing nonconductive surfactant, PEDOT: PTEB showed increasing film conductivity with increasing PTEB concentration. The result demonstrates the formation of efficient electrical conduction network formed by the fully conductive latex nanoparticles. The addition of PTEB for EDOT polymerization significantly reduced the size of composite particles, formed stable spherical particles, enhanced thermal stability, crystallinity, and conductivity of PEDOT:PTEB composite. Evidence from UV–VIS and FTIR measurement showed that strong molecular interaction between PTEB and PEDOT resulted in the doping of PEDOT chains. X‐ray analysis further demonstrated that PTEB chains were intercalated in the layered crystal structure of PEDOT. The emulsion polymerization of EDOT using conducting surfactant, PTEB demonstrated the synergistic effect of PTEB on colloid stability and intercalation doping of PEDOT during polymerization resulting in significant conductivity improvement of PEDOT composite nanoparticles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2536–2548, 2008     

Structural changes of silver polymer electrolytes: Comparison between poly(2‐ethyl‐2‐oxazoline) and poly(N‐vinyl pyrrolidone) complexes with silver salt

The difference between the polymer matrices of poly(2‐ethyl‐2‐oxazoline) (POZ) and poly(N‐vinyl pyrrolidone) (PVP) does not have a significant effect on the facilitated propylene transport and propylene solubility in 1:1 polymer/silver salt complex membranes, according to our previous work. In this article, its origin is investigated in terms of both microstructures of silver polymer electrolytes and the coordinative interaction of silver ion with polymer and with the counteranion. Initially different microstructures of POZ and PVP become similar to each other upon dissolving a large amount of silver salt, as evidenced by propane transport properties, specific volume, and Bragg d‐spacing. The dissolution of the silver salt in the polymer solvent strongly depends on the coordinative interaction between silver ion and carbonyl oxygen of POZ and PVP. Thus, the structural similarity upon dissolving silver salts in POZ and PVP is primarily determined by the coordinative interaction between silver ion and carbonyl oxygen, which was confirmed by theoretical structure calculation based on density functional theory and by IR and Raman spectroscopy. Therefore, facilitated olefin transport for silver polymer electrolyte membranes does not strongly depend on the polymeric matrix at high silver concentrations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 232–237, 2004     

Preparation of Ag nanoparticles termini‐protected side‐chain liquid crystalline azobenzene polymers by RAFT polymerization

A new synthetic approach to prepare Ag nanoparticles protected side‐chain liquid crystalline (LC) azobenzene polymers was reported. It is based on the reduction of silver ions in presence of a LC polymer polymerized by RAFT. The formation of Ag colloidal nanoparticles was confirmed by TEM and UV analysis. At the same time, according to the results of DSC, XPS, and FTIR spectra, Ag nanoparticles were protected by the side‐chain LC azobenzene polymers through surface attachment interactions between thiol groups and Ag. The out‐plane orientation of side‐chain LC is confirmed by surface‐enhanced Raman spectra analysis and scanning near‐field optical microscope, resulting from the large electromagnetic field arising from the excitation of surface plasmon polariton of Ag nanoparticles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5380–5386, 2007     

Synthesis of amphiphilic graft copolymer brush and its use as template film for the preparation of silver nanoparticles

A microphase‐separated, amphiphilic graft copolymer consisting of a poly (vinyl chloride) (PVC) backbone and poly(oxyethylene methacrylate) (POEM) side chains, (PVC‐g‐POEM at 62:38 wt %) was synthesized via atom transfer radical polymerization (ATRP). Nuclear magnetic resonance (¹H NMR), FTIR spectroscopy, and transmission electron microscopy (TEM) clearly revealed that the “grafting from” method using ATRP was successful and that the graft copolymer molecularly self‐assembled into discrete nanophase domains of continuous PVC and isolated POEM regions. The self‐assembled graft copolymer film was used to template the growth of silver nanoparticles in solid state by introducing a AgCF₃SO₃ precursor and a UV irradiation process. The in situ formation of silver nanoparticles in the graft copolymer template film was confirmed by TEM, UV–visible spectroscopy, and wide angle X‐ray scattering. FTIR spectroscopy and X‐ray photoelectron spectroscopy also demonstrated the selective incorporation and in situ formation of silver nanoparticles within the hydrophilic POEM domains, presumably due to strong interactions between the silver and the ether oxygen in POEM. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3911–3918, 2008     

Isothermal crystallization kinetics of polypropylene/POSS composites

Polypropylene (PP)/octavinyl polyhedral oligomeric silsesquioxane (POSS) composites were prepared by two different processing methods: reactive blending and physical blending, and the crystallization behavior of PP and PP/POSS composites was studied by means of differential scanning calorimetry and polarized optical microscope. The results showed that the crystallization of PP in PP/POSS composites was strongly influenced by the different processing methods. POSS particles can act as effective nucleating agent, accelerating the crystallization of PP. The crystallization rate increased more dramatically for the reactive blending composite due to the stronger nucleating effect of PP grafted POSS. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1762–1772, 2008     

Compatibilization effect of TiO2 nanoparticles on the phase structure of PET/PP/TiO2 nanocomposites

Polyethylene terephthalate (PET)/Polypropylene (PP)/TiO₂ nanocomposites were prepared by compounding a PP/TiO₂ nanocomposite premix with PET in absence and presence (up to 6 vol %) of maleic anhydride grafted polypropylene (PP‐g‐MA). In absence of PP‐g‐MA, the TiO₂ nanoparticles were mainly located at the PET/PP interface and to a lesser extent in the dispersed PET droplets. As the TiO₂ nanoparticles were coated by polyalcohol their surface could react with PP‐g‐MA and thus improving the compatibilization with PP. Therefore in presence of PP‐g‐MA the TiO₂ nanoparticles were preferentially located in the PP. The incorporated TiO₂ nanoparticles exerted a compatibilization effect on the PET/PP blend. Depending on the location of TiO₂ three different compatibilization mechanisms were proposed to be at work: (1) Locating at the interface, the TiO₂ nanoparticles decrease the free energy of mixing, and thus increase the thermodynamic stability of the nanocomposites; (2) The TiO₂ nanoparticles at the interface also prevent the coalescence of PET droplets; (3) Preferentially located in the PP matrix, the TiO₂ nanoparticles decreased the viscosity ratio which facilitated the droplet breakup of PET. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1616–1624, 2009     

Facile preparation of metal nanoparticle‐coated polystyrene beads by catechol conjugated polymer

A universal method to modify polystyrene beads (PSBs) is proposed, using the 2‐chloro‐3′,4′‐dihydroxyacetophenone (CCDP) quaternized to poly(ethylene glycol)‐g‐poly(dimethylaminethyl methacrylate) [PEG‐g‐PDMA, QC‐PEG]. In the study, CCDP of QC‐PEG is adhered onto PSBs under alkali condition, where polyvinyl pyrrolidone (PVP) has been added as stabilizer. The surface modified PSBs with QC‐PEG (QC‐PSBs) have been functionalized, by depositing silver nanoparticles (Ag‐PSBs) as antimicrobial, iron oxide nanoparticles (Fe‐PSBs) as magnet, and TiO₂ nanoparticles (Ti‐PSBs) as photo‐catalyst. Modification and functionalization of the obtained PSBs have been rectified by microscopy and spectroscopy investigations, including scanning electron microscope, X‐ray photoelectron microscope, and UV–vis spectrometer. The functionalized Ag‐PSBs show outstanding antimicrobial activities against gram‐positive and gram‐negative bacteria, due to their containing silver nanoparticles; while significant photo‐catalytic behavior was found against methylene blue, after depositing TiO₂ nanoparticles. The proposed universal modified PSBs will make a strong contribution in different fields, as a functional material. Copyright © 2014 John Wiley & Sons, Ltd.     

Organic/inorganic hybrid nanospheres coated with palladium/P4VP shells from surface‐initiated atom transfer radical polymerization

Crosslinked poly(4‐vinylbenzyl chloride) (PVBC) nanospheres of about 160 nm were first synthesized by emulsion copolymerization of 4‐vinylbenzyl chloride (VBC) in the presence of a crosslinking agent, p‐divinylbenzene. Subsequent modification of the nanosphere surfaces via surface‐initiated atom transfer radical polymerization of 4‐vinylpyridine, using the VBC units of PVBC on the nanosphere surface as the macroinitiators, produced a well‐defined and covalently tethered poly(4‐vinylpyridine) (P4VP) shells of 24–27 nm in thickness. Activation of the P4VP shells in a PdCl₂ solution, followed by reactions with CO or H₂S gas, gave rise to the corresponding P4VP composite shells containing densely dispersed palladium metal or palladium sulfide nanoparticles. The chemical composition of the nanosphere surfaces at various stages of surface modification was characterized by X‐ray photoelectron spectroscopy. Field emission scanning electron microscopy and transmission electron microscopy were used to characterize the morphology of the organic/inorganic hybrid nanospheres coated with palladium/P4VP shells. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2119–2131, 2008