Adsorption of Bovine Serum Albumin onto Polystyrene Latex Particles Bearing Saccharidic Moieties

The adsorption of bovine serum albumin (BSA) onto polystyrene latexes bearing various amounts of sugar moieties has been investigated as a function of pH and ionic strength and the results were compared to those for bare polystyrene latexes having negative surface charges. The functionalized latexes were produced by seeded copolymerization of (0.3 μm) liposaccharidic monomer onto polystyrene particles obtained by soap-free emulsion polymerization of styrene using potassium persulfate as initiator. At first, the electrophoretic mobility behavior of the various latexes was examined as a function of pH: a significant decrease was observed in the case of saccharide-containing latex particles compared to the bare particles. The adsorption of BSA onto these latexes exhibited a reduced amount of adsorbed BSA for those latex particles bearing saccharide groups. This adsorbed amount depends on the yield of saccharidic monomer incorporated onto the surfaces of the latex particles.     

Latex and hollow particles of reactive polypyrrole: preparation, properties, and decoration by gold nanospheres

Polypyrrole-coated polystyrene latex particles bearing reactive N-amino functional groups (PS-PPyNH2) were prepared by the in-situ copolymerization of pyrrole (Py) and the active amino-functionalized pyrrole (PyNH2) in the presence of 1.33 microm-diameter polystyrene (PS) latex particles. These particles were prepared by dispersion polymerization of styrene using poly(N-vinylpyrrolidone), PNVP, as a steric stabilizer. The functionalized polypyrrole-coated PS particles (PS-PPyNH2) were characterized in terms of their particle size and surface morphology using transmission electron microscopy (TEM). Infrared and X-ray photoelectron spectroscopy (XPS) detected pyrrole-NH2 repeat units at the surface of the latex particles, indicating that this monomer had indeed copolymerized with pyrrole. The core-shell structure of the PS-PPyNH2 particles was confirmed by etching the polystyrene core in THF, leading to the formation of hollow conducting polymer capsules. The PS-PPyNH2 particles were then decorated with citrate-stabilized gold nanoparticles via electrostatic interactions. Furthermore, etching of the polystyrene core resulted in the formation of gold-decorated PPyNH2 hollow capsules.     

Synthesis of amino‐functionalized latex particles by a multistep method

Cationic latex particles with surface amino groups were prepared by a multistep batch emulsion polymerization. In the first one or two steps, monodisperse cationic latex particles to be used as the seed were synthesized, and in the third step, two different amino‐functionalized monomers [aminoethylmethacrylate hydrochloride (AEMH) and vinylbenzylamine hydrochloride (VBAH)] were used to synthesize the final functionalized latex particles. 2,2′‐Azobisisobutyramidine dihydrochloride was used as the initiator, and different concentrations of two quaternary ammonium emulsifiers with hydrophobic chains of different lengths were examined. To characterize the final latexes yields were obtained gravimetrically, and particle size distributions and average particle diameters were determined by transmission electron microscopy and photon correlation spectroscopy. The amount of amino groups was determined by fluorimetry. The effect of the amino‐functional monomer used on the final latexes and the colloidal behavior of the system were studied. The influence of the different conditions utilized to synthesize the latexes on the colloidal stability of the particles was evaluated in terms of the Fuchs stability ratio and electrophoretic mobility. High yields of the amino‐functional monomers were obtained. Surface amino, amidine, and quaternary ammonium groups provided the cationic character. The colloidal stability behavior of the products obtained was compatible with their cationic character. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2929–2936, 2001     

Polymerization of vinyl monomers in the presence of silica having surface functional groups

The surface of silica was modified by mercaptopropyl, chloropropyl, aminopropyl, and methacryloxypropyl groups by the treatment of silica with the corresponding silane coupling agents, and the effects of functional groups on the surface on the polymerization of vinyl monomers initiated by benzoyl peroxide or 2,2-azobisisobutyronitrile were investigated. Although the rate of the polymerization of vinyl monomers in the presence of silica was almost equal to that in the absence of silica, a part of polymer formed was grafted onto silica surface. The polymerization was considerably retarded in the presence of these functionalized silicas and the corresponding polymers were effectively grafted onto the surface. The molecular weight of ungrafted polymer formed in the presence of the functionalized silica was lower than that formed in the presence of unmodified silica. This indicates that the chain transfer reaction of growing polymer radical to functionalized silica surface forms radicals on the surface, which then couples with growing polymer radical and/or reinitiates the polymerization to give rise to the grafting of polymers onto the surface. In the case of silica having methacryloxypropyl groups, the grafting based on the copolymerization of vinyl monomer with the surface methacryloxypropyl groups was considered to successfully proceed.     

Effect of polymerization conditions on the molecular weight of polystyrene grafted onto silica in the radical graft polymerization initiated by azo or peroxyester groups introduced onto the surface

The effect of polymerization conditions on the molecular weight of polystyrene grafted onto silica obtained from the radical graft polymerization initiated by azo and peroxyester groups introduced onto the surface was investigated. The molecular weight of polystyrene grafted onto silica obtained from the radical graft polymerization initiated by surface azo and peroxyester groups decreased with decreasing monomer concentration and polymerization temperature. The molecular weight of polystyrene was found to be controlled to some extent by the addition of a chain transfer agent. The molecular weight of grafted chain on silica surface obtained from the graft polymerization initiated by surface radicals formed by photodecomposition of azo groups was considerably smaller than that by thermal decomposition. The number of grafted polystyrene in photopolymeriztion, however, was much larger than that in thermal polymerization. These results are explained by the blocking of surface radicals formed on the silica surface by previously grafted polymer chain: when the decomposition of surface azo and peroxyester groups proceed instantaneously at the initial stage of the polymerization, the number of grafted polymer chains increased.     

阴离子型接枝微粒PDAC/PSA的制备及对谷氨酸的吸附性能初探

采用自由基聚合法在溶液聚合体系中将功能单体丙烯酰氧乙基三甲基氯化铵(DAC)接枝于聚苯乙烯伯胺微球(PSA)表面,制备了接枝微粒PDAC/PSA,考察了主要因素对接枝聚合的影响,并初步探究了其对L-谷氨酸的吸附特性。结果表明,在反应温度25℃、单体质量分数为6%、引发剂占单体质量的1.2%的条件下,可制得接枝度为431mg/g的接枝微粒,其对L-谷氨酸的吸附量达140mg/g。     

Acetal-functionalized polymer particles useful for immunoassays

The synthesis of core-shell type polystyrene monodisperse particles with surface acetal groups was carried out by a two-step emulsion polymerization process. In a first step, the core was synthesized by batch emulsion polymerization of styrene (St), and in the second step, the shell was polymerized by batch emulsion terpolymerization of styrene, methacrylic acid (MAA), and methacrylamidoacetaldehyde dimethyl acetal (MAAMA), using the seed obtained previously. With the aim of analyzing the effect of the thickness of the shell, the pH of the reaction medium and the weight ratio of the termonomers to prepare the shell, on the amount of the functionalized groups, several core-shell type latex particles were synthesized by two-step emulsion polymerization in a batch reactor. The latexes were characterized by TEM and conductimetric titration to obtain the particle size distribution and the amount of carboxyl and acetal groups on the surface, respectively. Looking for the applicability of the synthesized latexes in immunoassays, IgG a-CRP rabbit antibody was covalently bonded to the surface of the particles synthesized in neutral medium. The complex latex-protein was immunologically active against the CRP antigen. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1605–1610, 1997     

Acetal‐functionalized polymer particles useful for immunoassays. II. Surface and colloidal characterization

Monodisperse polymer colloids with dimethyl and diethyl acetal functionalities were synthesized by a two‐step emulsion polymerization process. The first step consisted of a batch emulsion homopolymerization of styrene (St). The dimethyl and diethyl acetal functionalities were obtained by batch emulsion terpolymerization of St, methacrylic acid (MAA), and methacrylamidoacetaldehyde dimethyl acetal (MAAMA) or methacrylamidoacetaldehyde diethyl acetal (MAADA) in the second step, onto the previously formed polystyrene latex particles. The latexes were characterized by TEM and conductimetric titration, in order to obtain the particle size distribution and the amount of carboxyl and acetal groups on the surface, respectively. The chemical stability of the functionalized surface groups during the storage time was analyzed. The hydrophilic character of the surface of the polymer particles was determined by means of nonionic emulsifier titration. The colloidal stability of the synthesized latexes was studied by measuring the critical coagulation concentration (CCC) against KBr electrolyte, and the existence of a hairy layer on the surface of the latex particles was analyzed by measuring the hydrodynamic particle diameter at several electrolyte concentrations. The surface functionalized groups remained stable for 2 years. The relative hydrophilic character and the colloidal stability were affected by the pH of the medium. On the other hand, the higher the surface charge, the larger the thickness of the hairy layer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 501–511, 1999     

Synthesis of core-shell type polystyrene monodisperse particles with chloromethyl groups

The synthesis of core-shell type polystyrene monodisperse particles with surface chloromethyl groups was carried out by a two-step emulsion polymerization process at different reaction temperatures. In a first step, the core was synthesized at 90 °C by means of batch emulsion polymerization of styrene (St), and in the second step, the shell was polymerized by batch emulsion copolymerization of St and chloromethylstyrene (CMS) using the seed obtained previously. With the aim of optimizing the production of these core-shell type polystyrene monodisperse particles with surface chloromethyl groups, the reaction temperature in the second step, the purification or not of the functionalized monomer (CMS), the amount and type of the redox initiator system used, and the type of addition of the initiator system to the reactor were studied.     

Facile preparation of monodisperse hollow cross‐linked chitosan microspheres

We have successfully prepared biocompatible and biodegradable hollow microspheres using carboxyl‐functionalized polystyrene particles as core template and the chitosan cross‐linked with glutaraldehyde as the shell. The monodisperse carboxyl‐functionalized polystyrene particles were made by emulsifier‐free emulsion polymerization. The structure, morphology, and constitution of the carboxyl‐functionalized polystyrene particles were characterized by FTIR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X‐ray photoelectron spectroscopy (XPS). The structure, morphology, and formation process of the hollow cross‐linked chitosan microspheres were characterized by FTIR, SEM, and TEM. The results revealed that the latex particles were removed by exposed to solvent and the microspheres exhibited the hollow structure. This work confirmed that the hollow microspheres were accomplished by fabricating on the basis of chemical cross‐linking on the surface of the carboxyl‐functionalized polystyrene particles and then removing off the cores of particles. Moreover, with the increase of carboxyl‐functionalization degree at the surface of latexes and the increase of cross‐linking period, the thicker and firmer monodisperse hollow microspheres were obtained. In addition, a water‐soluble drug, salicylic acid, encapsulated in the microcapsules slowly released at pH 1.2. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 228–237, 2008     

Polymer mediated peptide immobilization onto amino-containing N-isopropylacrylamide-styrene core-shell particles

Monodisperse cationic core-shell latex particles have been prepared using a shot polymerization process, with N-(3-aminopropyl)-methacrylamide-hydrochloride (APMH) as the functional monomer. The final latexes were characterized with respect to final polymerization conversion, water soluble polymer formation, particle size and size distribution, surface charge density and electrokinetic properties. Then the covalent grafting of maleic anhydride-alt-methyl vinyl ether (MAMVE) copolymer onto aminated latex particles was investigated. The most efficient conditions to obtain derivatised particles with no alteration of the colloidal stability were to control both polymer amount/latex particles concentration ratio and the mixing method of the two species. The charge inversion of the hydrolysed MAMVE functionalized particles was demonstrated by measuring the electrophoretic mobility as a function of pH. Finally, the covalent binding approach was implemented with peptide-MAMVE conjugates, confirming the great potential of this promising methodology for the preparation of reactive latex particles bearing peptides.     

Cationic Grafting of Vinyl Polymers onto a Carbon Whisker,Initiated by Acylium Perchlorate Groups Introduced onto the Surface

Abstract

The cationic graft polymerization of vinyl monomers onto a carbon whisker, vapor-grown carbon fiber, initiated by acylium perchlorate groups introduced onto the surface, was investigated. The introduction of acylium perchlorate groups onto a carbon whisker was achieved by the treatment of a carbon whisker having acyl chloride groups, which were introduced by the reaction of surface carboxyl groups with thionyl chloride, with silver perchlorate in nitrobenzene. It was found that the cationic polymerization of vinyl monomers, such as styrene, indene, N-vinyl-2-pyrrolidone, and n-butyl vinyl ether, is initiated by acylium perchlorate groups on a carbon whisker. In the polymerization, the corresponding vinyl polymers were grafted onto a carbon-whisker surface based on the propagation of polymer from the surface: the percentage of grafting of polystyrene and polyindene reached 42.5 and 100.3%, respectively. The percentage of polystyrene grafting decreased with increasing polymerization temperature because of preferential chain transfer reactions at higher temperatures. Polymer-grafted carbon whisker gave a stable colloidal dispersion in a good solvent for grafted polymer.     

Preparation and characterization of cationic polystyrene latex particles of different aminated surface charges

Functionalized polystyrene latex particles were obtained either by seed particle functionalization or by the shot-growth procedure using 2,2′-azobis (2-amidino-propane) dihydrochloride as an initiator and vinylbenzylamine hydrochloride as a cationic monomer. The capabilities of both processes to produce functionalized particles in terms of functionalization yields coming from surface amino group titrations were compared. Different titration methods were performed and a new technique was introduced using fluorescamine.     

Synthesis of Latex Particles with Surface Functional Groups and Their Applications for the Fabrication of Porous Materials

In this study, monodisperse latex particles with specific surface functional groups were synthesized by emulsifier-free emulsion polymerization. Amidine or carboxylated polystyrene nanospheres with narrow size distribution were prepared by emulsion polymerization using AIBA (α,α′-zodiisobutyramidine dihydrochloride) as amine-containing initiator or acrylic acid as carboxyl-containing comonomer, respectively. Factors affecting the particle size and distribution were systemically studied by changing the amount of initiator or monomer, the polymerization temperature, and the stirring speed of emulsion polymerization reactor. Monodisperse polymethylmethacrylate beads were also synthesized by soapless emulsion polymerization using methacrylic acid or aminoethylmethacrylate hydrogen hydrochloride as comonomer for the surface functionalization of the particles. As applications of the latex beads, the polymeric particles were adopted as templating materials for the fabrication of macroporous titania film and meso-macroporous silica particles by colloidal templating method.     

Surface modification of monodisperse hydroxyl functionalized polymeric microspheres using ceric ammonium nitrate

The surface modification of monodisperse hydroxyl functionalized polymeric microspheres was carried out by utilizing a redox initiation system. Styrene, divinylbenzene and hydroxyethyl methacrylate were used as the second monomer in the seeded polymerization. An excessive amount of the second monomer emulsion was swollen into the polystyrene (PS) seed particles completely by controlling the medium solvency and swelling temperature. The hydroxyl functional groups were radicalized by the ceric ammonium nitrate in nitric acid solution, and the methyl methacrylate was reacted uniformly on the surface of microspheres. From the SEM, and FE-TEM measurements, highly monodisperse microspheres having a smooth surface, and polymethylmethacrylate (PMMA) coating layer were observed, respectively. The surface characteristics of the PS seed particles, hydroxyl functionalized and surface-modified polymeric microspheres were confirmed by utilizing FT-IR, XPS and thermal analysis.     

Effect of hydrophilic comonomer and surfactant type on the colloidal stability and size distribution of carboxyl- and amino-functionalized polystyrene particles prepared by miniemulsion polymerization

Carboxyl and amino-functionalized polystyrene latex particles were synthesized by the miniemulsion copolymerization of styrene and acrylic acid or 2-aminoethyl methacrylate hydrochloride (AEMH). The reaction was started by using an oil-soluble initiator, such as 2,2'-azobis(2-methylbutyronitrile) (V-59). The effect of the functional monomer content and type of surfactant (non-ionic versus ionic) on the particle size and particle size distribution was investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). A bimodal particle size distribution was observed for functionalized latex particles prepared in the presence of the non-ionic surfactant (i.e., Lutensol AT-50) when 1 wt % of acrylic acid or 3 wt % of AEMH as a comonomer was employed. The copolymer particle nucleation was studied by using a highly hydrophobic fluorescent dye. From the obtained results, the formation of bimodal particle size distribution may be attributed to a budding-like effect, which takes place during the earlier stage of polymerization and is caused by the additional stabilizing energy originated from the ionic groups of a functional polymer. The reaction mechanism of particle formation in the presence of non-ionic and ionic surfactants has been proposed. The amount of the surface functional groups was determined from polyelectrolyte titration data.     

Graft polymerization of vinyl monomers onto nanosized alumina particles

To enhance the interfacial interaction in alumina nanoparticles filled polymer composites, an effective surface modification method was developed by grafting polystyrene and polyacrylamide onto the particles. That is, the alumina surface was firstly treated with silane, followed by radical grafting polymerization in aqueous or non-aqueous systems. Results of infrared spectroscopy and dispersiveness in solvents demonstrated that the desired polymer chains have been covalently bonded to the surface of the alumina particles. They also greatly changed their surface characteristics. In addition, effects of polymerization conditions, including ways of monomer feeding, concentrations of monomer and initiator, and reaction time, on the grafting reaction were presented. It was found that the growing polymer radicals and/or the grafted polymer chains had a blocking effect on the diffusion of radicals or monomers towards the surface of nanoalumina. This was due to the fact that the interaction between the solvent and the grafted polymers was weaker than that between the grafted polymers and the nanoparticles.     

ABC type miktoarm star copolymers through combination of controlled polymerization techniques with thiol‐ene and azide‐alkyne click reactions

ABC type miktoarm star copolymer with polystyrene (PS), poly(ε‐caprolactone) (PCL) and poly(ethylene glycol) (PEG) arms was synthesized using controlled polymerization techniques in combination with thiol‐ene and copper catalyzed azide‐alyne “click” reactions (CuAAC) and characterized. For this purpose, 1‐(allyloxy)‐3‐azidopropan‐2‐ol was synthesized as the core component in a one‐step reaction with high yields (96%). Independently, ω‐thiol functionalized polystyrene (PS‐SH) was synthesized in a two‐step protocol with a very narrow molecular weight distribution. The bromo end function of PS obtained by atom transfer radical polymerization was first converted to xanthate function and then reacted with 1, 2‐ethandithiol to yield desired thiol functional polymer (PS‐SH). The obtained polymer was grafted onto the core by thiol‐ene click chemistry. In the following stage, ε‐caprolactone monomer was polymerized from the core by ring opening polymerization (ROP) using tin octoate as catalyst through hydroxyl groups to form the second arm. Finally, PEG‐acetylene, which was simply synthesized by the esterification of Me‐PEG and 5‐pentynoic acid, was clicked onto the core through azide groups present in the structure. The intermediates at various stages and the final miktoarm star copolymer were characterized by ¹H NMR, FTIR, and GPC measurements. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Surface modification of crosslinked poly(styrene-divinyl benzene) micrometer-sized particles of narrow size distribution by ozonolysis

Micrometer-sized polystyrene template particles of narrow size distribution were prepared by dispersion polymerization of styrene in 2-methoxyethanol. Uniform micrometer-sized polystyrene/crosslinked poly(styrene-divinyl benzene) composite particles were formed by a single-step swelling process of the template particles with styrene, divinyl benzene and benzoyl peroxide, followed by polymerization at 70 degrees C. Uniform micrometer-sized crosslinked poly(styrene-divinyl benzene) particles of higher surface area were produced by dissolution of the template polystyrene part of the former composite particles with N,N-dimethylformamide. Hydroperoxide conjugated crosslinked poly(styrene-divinyl benzene) particles were produced by ozonolysis of these particles. The effect of ozonolysis conditions, such as exposure time and flow rate of the ozone, on the hydroperoxide conjugation to the crosslinked particles was also studied. Functionalization of the crosslinked poly(styrene-divinyl benzene) particles was performed by graft polymerization of vinylic monomers such as acrylonitrile and chloromethylstyrene on the hydroperoxide conjugated crosslinked particles. This was accomplished by raising the temperature (e.g., 70 degrees C) of deairated acetonitrile dispersions containing the hydroperoxide conjugated particles and the vinylic monomers. The influence of various polymerization parameters on the grafting yield, e.g., monomer concentration, conjugated hydroperoxide concentration, and temperature, was also elucidated.     

Functionalization of three‐dimensionally ordered macroporous cross‐linked polystyrene by atom‐transfer radical polymerization of hydroxyethyl methacrylate and subsequent derivatization

The surface‐initiated atom‐transfer radical polymerization (ATRP) technique was applied to the graft polymerization of 2‐hydroxyethyl methacrylate (HEMA) from three‐dimensionally ordered macroporous crosslinked polystyrene (3DOM CLPS) on which the initiator (benzyl chloride) was immobilized onto the pore wall of 3DOM CLPS by chloromethylation of benzene ring. By the adjustment of the monomer concentration or graft polymerization time, the thickness of grafted polymer layers can be controlled. FTIR analysis confirms that the graft polymerization of HEMA via ATRP had been taken place at the pore wall of 3DOM CLPS. SEM images of PHEMA‐grafted 3DOM CLPS show that the ordered structure is well preserved after graft polymerization and the grafted layers are dense and homogeneous. The maximum thickness of grafted layer is up to 35 nm and the corresponding percent weight increase is 102.8% in this study. Moreover, the PHEMA layers were further functionalized in high yield via their reactive hydroxyl groups under gentle condition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7950–7959, 2008