Realizing porphyrin‐functionalization of crosslinked polystyrene microspheres via two special polymer reactions

A novel route to make crosslinked polystyrene (CPS) microspheres to be porphyrin‐functionalized via two special polymer reactions, Kornblum reaction and Adler reaction, was designed and founded. The chloromethyl groups of chloromethylated crosslinked polystyrene (CMCPS) microspheres were first oxidized to aldehyde groups by dimethyl sulfoxide as oxidant via Kornblum oxidation reaction, obtaining aldehyde group‐modified microspheres, ALCPS microspheres, in which, a great quantity of benzaldehyde groups suspend from the main chain, and the effects of the main factors including the reaction temperature, the addition of KI as catalyst and the used amount of NaHCO₃ as acid acceptor on the oxidation reaction were examined. Subsequently, the synchronic synthesizing and immobilizing of porphyrins on CPS microspheres were carried out via the Adler reaction between solid and liquid phases, in which, ALCPS microspheres, pyrrole and benzaldehyde or benzaldehyde analog in a solution were used as co‐reactants, resulting in porphyrin‐functionalized microspheres, and the influence of diverse factors including the acidity of the protonic acid catalyst, the substituent structure of benzaldehyde analog, and the polarity of the solvent as well as the swelling property of the solvent for CPS microspheres on the process of synchronously synthesizing and immobilizing porphyrins on CPS microspheres were investigated in depth. The experimental results indicate that via the designed route, the porphyrin‐functionalization of CPS microspheres can successfully be realized. For the Kornblum oxidation reaction, under the optimal reaction conditions, the conversion of chloromethyl groups can reach 90%. For the Adler reaction between solid and liquid phases, the fitting protonic acid catalyst is lactic acid, appropriate solvent is a mixture of dimethyl sulfoxide and xylene, and using 4‐chlorobenzaldehyde as a benzaldehyde analog reactant in the solution is in favor of the porphyrin‐functionalization of CPS microspheres. Under these specific conditions, the immobilized amount of porphyrin can get up to 23.33 mmol/100 g. Copyright © 2011 John Wiley & Sons, Ltd.     

Functionalized Natural Carbon‐Supported Nanoparticles as Excellent Catalysts for Hydrocarbon Production

We report a one‐pot and eco‐friendly synthesis of carbon‐supported cobalt nanoparticles, achieved by carbonization of waste biomass (rice bran) with a cobalt source. The functionalized biomass provides carbon microspheres as excellent catalyst support, forming a unique interface between hydrophobic and hydrophilic groups. The latter, involving hydroxyl and amino groups, can catch much more active cobalt nanoparticles on surface for Fischer–Tropsch synthesis than chemical carbon. The loading amount of cobalt on the final catalyst is much higher than that prepared with a chemical carbon source, such as glucose. The proposed concept of using a functionalized natural carbon source shows great potential compared with conventional carbon sources, and will be meaningful for other fields concerning carbon support, such as heterogeneous catalysis or electrochemical fields.     

One‐Step Preparation of Multifunctional Chitosan Microspheres by a Simple Sonochemical Method

Chitosan is a biodegradable natural polymer with great potential for pharmaceutical applications due to its biocompatibility, high charge density, nontoxicity, and mucoadhesion properties. Processing techniques for the preparation of chitosan microspheres have been extensively developed since the 1980s. The present paper describes for the first time a fast and one‐step process for the preparation of stable chitosan microspheres by a simple sonochemical method. The microspheres were characterized by their particle size, surface morphology, stability, and drug‐entrapment efficiency. The average size of the microspheres was found to be around 1 μm with a narrow size distribution, which enabled them to be used for in vivo applications. The encapsulation of different dyes into these microspheres was readily achieved with more than 75 % efficacy by dissolving them into the organic phase before sonication. The chitosan microspheres demonstrated excellent stability toward acidic and basic conditions ranging from pH 4 to 9, thereby indicating their implementation as possible therapeutic and diagnostic agents. The stability of these microspheres appears to be contributed from intermolecular imine cross‐linking in addition to other noncovalent interactions. The ability of the surface‐exposed amino groups of chitosan microspheres to undergo chemical conjugation with potential drugs and/or targeting vectors was determined by their reaction with fluorescein isothiocyanate (FITC) and fluorescamine followed by confocal microscopy.     

Determination of amine and aldehyde surface densities: application to the study of aged plasma treated polyethylene films

The aim of this work was to test and to compare different methods reported in the literature to quantify amine and aldehyde functions on the surface of polyethylene (PE) films treated by ammonia plasma and to specify their stability against time. A low pressure ammonia plasma reactor was used to functionalize PE films with amine groups, which could be subsequently used for further immobilization of biomolecules. In order to determine the density of amine groups on the surface of treated films, various molecule probes and spectrophotometric analytical methods have been investigated. Two methods using (i) sulfosuccinimidyl 6-[3'-(2-pyridyldithio)-propionamido] hexanoate (sulfo-LC-SPDP) and (ii) 2-iminothiolane (ITL) associated with bicinchoninic acid (BCA) have been proved to be reliable and sensitive enough to estimate the surface concentration of primary amine functions. The amount of primary amino groups on the functionalized polyethylene films was found to be between 1.2 and 1.4 molecules/nm2. In a second step, the surface concentration of glutaraldehyde (GA), which is currently used as a spacer arm before immobilization of biomolecules, has been assessed: two methods were used to determine the surface density of available aldehyde functions, after the reaction of GA with the aminated polyethylene film. The concentration of GA was found to be in the same range as primary amine concentration. The influence of aging time on the density of available amino and aldehyde groups on the surfaces were evaluated under different storage conditions. The results showed that 50% of the initial density of primary amine functions remained available after storage during 6 days of the PE samples in PBS (pH 7.6) at 4 degrees C. In the case of aldehyde groups, the same percentage of the initial density (50%) remained active after storage in air at RT over a longer period, i.e., 15 days.     

Covalent immobilization of albumin on micron‐sized magnetic poly(methyl methacrylate‐divinylbenzene‐glycidyl methacrylate) microspheres prepared by modified suspension polymerization

Micron‐sized magnetic poly(methyl methacrylate‐divinylbenzene‐glycidyl methacrylate) microspheres were prepared by a modified suspension polymerization in the presence of oleic acid‐coated magnetite nanoparticles. The magnetic microspheres were functionalized by reacting the epoxy groups with ammonia solution to provide amino groups. After activated with glutaraldehyde (GA), bovine serum albumin was covalently immobilized on these magnetic microspheres. The influence of initial protein concentration, pH and ionic strength of the protein solution on covalent immobilization was studied. Scanning electron micrographs showed that the magnetic microspheres had an average size of 6.4 µm and relative narrow size distribution. Magnetic measurement revealed the magnetic microspheres were superparamagetic with saturation magnetization of 7.32 emu/g. The successful amination of the magnetic microspheres was confirmed by Fourier transform infrared spectroscopy (FT‐IR). Copyright © 2005 John Wiley & Sons, Ltd.     

Surface acidity and basicity of functionalized silica particles

Tetraethoxysilane has been co-hydrolyzed with functionalized organosilanes in a modified Stöber process to produce silica particles with amino, carboxylate or dihydroimidazole groups on the surface. The effects of reaction conditions and the loading of the functionalized organosilane on particle size was examined by TEM. Fluorescence spectroscopy of the surface amino groups covalently modified with fluorescamine, and the surface carboxylate groups with 4-bromomethyl-6,7-dimethoxycoumarin, demonstrated that these functional groups were accessible for further reaction. Changes in surface acidity and basicity caused by the presence of functional groups (amine, dihydroimidazole, carboxylate) on the particle surface were determined using an indicator titration technique. Particles with surface imidazole and amine groups and particles with surface carboxylate groups have enhanced basicity and acidity, respectively. Dihydroimidazole-modified silica had greater surface basicity than the amine-modified silica. The effect on basicity and acidity increases as the amount of added functionalized silane increases. However, this increase is nonlinear with respect to the increase in added functionalized silane. Particles with both surface dihydroimidazole and carboxylate groups demonstrated reduced surface basicity and acidity.     

Preparation of Amino-functionalized Multiwall Carbon Nanotube/Gold Nanoparticle Composites

Multiwall carbon nanotubes (MWNT) were modified orderly with carboxyl groups and amino groups. The MWNT/gold nanoparticle composites were formed when the amino‐functionalized MWNT was interacted with gold colloids. The functionalized MWNT was characterized using Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. The amino‐functionalized MWNT allows further attaching gold nanoparticles through electrostatic interaction between the negatively charged gold nanoparticles and amino groups on the surface of the MWNT. The composite of gold nanoprticles and amino‐functionalized MWNT was characterized by transmission electron microscopy. This method decorating carbon nanotubes can be used to identify the location of functional groups, i.e. defect sites on carbon nanotubes.     

Phosphate-functionalized magnetic microspheres for immobilization of Zr ions for selective enrichment of the phosphopeptides

In this work, we developed phosphate functionalized magnetic Fe₃O₄@C microspheres to immobilize Zr⁴⁺ ions for selective extraction and concentration of phosphopeptides for mass spectrometry analysis. Firstly, we synthesized Fe₃O₄@C magnetic microspheres as our previous work reported. Then, the microspheres were functionalized with phosphate groups through a simple hydrolysis reaction using 3-(trihydroxysilyl)propyl methylphosphate. And the Zr⁴⁺ ions were immobilized on phosphate-functionalized magnetic microspheres by using phosphate chelator. Finally, we successfully employed Zr⁴⁺-phosphate functionalized magnetic microspheres to selectively isolate the phosphopeptides from tryptic digests of standard protein and real samples including rat brain. All the experimental results demonstrate the enrichment efficiency and selectivity of the method we reported here.     

Biohybrid nanogels by crosslinking of ovalbumin with reactive star‐PEGs in W/O emulsions

This article reports the synthesis of biohybrid nanogels by crosslinking six‐arm acrylate functionalized star shaped P(EO‐stat‐PO) with the amine groups of various amino acids of a hen egg ovalbumin in W/O emulsion. PEG Poly(ethylene glycol)‐diamines of different molecular weights (368.5 g/mol, 897.1 g/mol, 3000 g/mol, and 6000 g/mol) were used to optimize the crosslinking reactions in aqueous droplets. The increase of molecular weight of the PEG‐diamine led to decrease of the nanogel size due to better stabilization by longer PEG chains. The size of the ovalbumin nanogels was independent of the acrylate‐sP(EO‐stat‐PO):ovalbumin ratio in the reaction mixture. The bicinchoninic acid (BCA) assay proved that the ovalbumin has been effectively crosslinked by reactive prepolymers. From the results of BCA assay, it can also be established that there exists a limiting amount of ovalbumin which can be incorporated into the nanogels. Both Diamine and ovalbumin‐based nanogels exhibit amphoteric behavior and display a positive charge in acidic and a negative charge in basic environment. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

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     

Preparation and characterization of monodisperse porous silica microspheres with controllable morphology and structure

A novel method for the preparation of monodisperse porous silica microspheres with controllable morphology and structure is reported. The starting porous polymer microspheres were first functionalized with ethylenediamine (EDA) to generate amino groups. Subsequently, silica nanoparticles were deposited in the porous polymer microsphere to form polymer/silica hybrid microspheres via a modified sol‐gel process in the presence of tetra‐n‐butylammonium bromide (TBAB) or tetramethyl ammonium hydroxide (TMAH). Upon calcination of the polymer/silica hybrid microspheres, the porous silica microspheres were obtained. The morphology, inner structure, and properties of the porous silica microspheres were studied by field emission scanning electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, and mercury intrusion method. The results show that the presence of TBAB or TMAH in the process not only prevents the agglomeration of the hybrid microspheres, but also governs the controllable morphology from a porous inner structure to a hollow‐cage structure. The obtained porous silica microspheres exhibit no shrinkage from the polymer microspheres with a yield of around 98%. These porous silica microspheres have potential applications in the fields of chromatography, catalyst, and biology. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polysiloxane microspheres functionalized with imidazole groups as a palladium catalyst support

Polysiloxane microspheres containing a large number of silanol groups were obtained by an emulsion process of modified polyhydromethylsiloxane. N‐substituted imidazole groups were grafted on these microspheres by the silylation of their silanol groups with N‐[γ‐(dimethylchlorosilyl)propyl]imidazole hydrochloride. The progress of the reaction was monitored using ²⁹Si and ¹³C magic angle spinning (MAS) NMR and its impact on microsphere morphology was studied using scanning electron microscopy (SEM). The usefulness of the imidazole‐functionalized microspheres as a support for a metal catalyst was demonstrated by their reaction with PdCl₂(PhCN)₂. In this way a new heterogenized catalyst, Pd(II) complex with imidazole ligands supported on polysiloxane microspheres, was generated. This catalyst, MPd , was characterized using ¹³C and ²⁹Si MAS NMR, X‐ray photoelectron, Fourier transform infrared and far‐infrared spectroscopies, X‐ray diffraction, SEM–energy‐dispersive X‐ray spectroscopy and wide‐angle X‐ray scattering. The catalyst appears in two structures, as Pd(II) complex and Pd(0) nanoclusters. Its catalytic activity was tested using a model reaction, the hydrogenation of cinnamaldehyde, and compared with that of an analogous complex operating in a homogeneous system. MPd showed a high activity in the promotion of hydrogenation of cinnamaldehyde. The activity in the substrate conversion was stable at least in five cycles of this reaction. The main product was hydrocinnamaldehyde which could be obtained with a yield above 70%. A mechanism of the reaction is proposed. Copyright © 2016 John Wiley & Sons, Ltd.     

Hydrophilic dual‐responsive magnetite/PMAA core/shell microspheres with high magnetic susceptibility and ph sensitivity via distillation‐precipitation polymerization

A facile and effective approach to preparation of dual‐responsive magnetic core/shell composite microspheres is reported. The magnetite(Fe₃O₄)/poly(methacrylic acid) (PMAA) composite microspheres were synthesized through encapsulating γ‐methacryloxypropyltrimethoxysilane (MPS)‐modified magnetite colloid nanocrystal clusters (MCNCs) with crosslinked PMAA shell. First, the 200‐nm‐sized MCNCs were fabricated through solvothermal reaction, and then the MCNCs were modified with MPS to form active vinyl groups on the surface of MCNCs, and finally, a pH‐responsive shell of PMAA was coated onto the surface of MCNCs by distillation‐precipitation polymerization. The transmission electron microscopy (TEM) and vibrating sample magnetometer characterization showed that the obtained composite microspheres had well‐defined core/shell structure and high saturation magnetization value (35 emu/g). The experimental results indicated that the thickness and degree of crosslinking of PMAA shell could be well‐controlled. The pH‐induced change in size exhibited by the core/shell microspheres reflected the PMAA shell contained large amount of carboxyl groups. The carboxyl groups and high saturation magnetization make these microspheres have a great potential in biomolecule separation and drug carriers. Moreover, we also demonstrated that other magnetic polymeric microspheres, such as Fe₃O₄/PAA, Fe₃O₄/PAM, and Fe₃O₄/PNIPAM, could be synthesized by this approach. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Decyl‐perfluorinated magnetic mesoporous microspheres for extraction and analysis perfluorinated compounds in water using ultrahigh‐performance liquid chromatography–mass spectrometry

In this work, the interior‐walls decyl‐perfluorinated functionalized magnetic mesoporous microspheres (F₁₇–Fe₃O₄@mSiO₂) were synthesized for the first time, and applied as adsorbents to extract and concentrate perfluorinated compounds (PFCs) from water samples. The fluorous functionalized interior pore‐walls contributed to the high‐selective preconcentration of PFCs due to fluorous affinity; and abundant silanol groups on the exterior surface of microspheres contributed to the good dispersibility in water sample. Four kinds of PFCs were selected as model analytes, including perfluorooctanoic acid, perfluorononanoic acid, perfluorododecanoic acid, and perfluorooctane sulphonate. In addition, UHPLC‐ESI/MS/MS was introduced to the fast and sensitive detection of the analytes after sample pretreatment. Important parameters of the extraction procedure were optimized, including salinity, eluting solvent, the amount of F₁₇–Fe₃O₄@mSiO₂ microspheres, and extraction time. The optimized procedure took only 10 min to extract analytes with high recoveries and merely 800‐μL acetonitrile to elute analytes from the magnetic adsorbents. Validation experiments showed good linearity (0.994–0.998), precision (2.6–7.6%), high recovery (93.4–105.7%) of the proposed method, and the limits of detection were from 0.008 to 0.125 μg/L. The F₁₇–Fe₃O₄@mSiO₂ magnetic microspheres have the advantages of great dispersibility in aqueous solution, high specificity of extraction, large surface area, and efficient separation ability. The results showed that the proposed method based on F₁₇–Fe₃O₄@mSiO₂ microspheres is a simple, fast, and sensitive tool for the analysis of PFCs in water sample.     

Preparation of silica microspheres with a broad pore size distribution and their use as the support for a coated cellulose derivative chiral stationary phase

A templating strategy using crosslinked and functionalized polymeric beads to synthesize silica microspheres with a broad pore size distribution has been developed. The polymer/silica hybrid microspheres were prepared by utilizing the combination of a templating weak cation exchange resin, a structure‐directing agent N‐trimethoxysilylpropyl‐N,N,N‐trimethylammonium chloride, and a silica precursor tetraethyl orthosilicate. The silica microspheres were then obtained after calcinating the hybrid microspheres. The as‐prepared materials were characterized by scanning electron microscopy, mercury intrusion porosimeter, and thermal gravimetric analysis. The results showed that the starting templating beads were about 5 μm in diameter and the formed silica microspheres were less than 3 μm with a pore size range of 10–150 nm, some pores were even extended to beyond 250 nm. It was demonstrated that cellulose tris(3,5‐dimethylphenylcarbamate) was readily coated onto the surface of the as‐synthesized silica microspheres without any additional surface pretreatment. The coated silica microspheres were uniformly dispersed even with high loading of the chiral stationary phase, which exhibited high resolution chiral separations in high‐performance liquid chromatography.     

Boronic acid functionalized Fe3O4 magnetic microspheres for the specific enrichment of glycoproteins

Glycoproteins are useful biomarkers and therapeutic targets for a number of diseases, including infections and cancer. However, identification and isolation of low‐abundant glycoproteins remains a significant challenge that limits their application. Thus, methods of specific and selective glycoprotein enrichment are required. In this study, novel phenylboronic acid functionalized magnetic microspheres were successfully synthesized. Fe₃O₄ microspheres were synthesized by using a hydrothermal method and were coated with tetraethyl orthosilicate using an ultrasonic method to form a core‐shell structure. Compared to the conventional mechanical stirring for 12 h, the ultrasonic method saved about 7 h in processing time, and the home‐made magnetic microspheres had better dispersibility and homogeneity. Subsequently, the magnetic microspheres were modified by addition of an amino group and a carboxyl group, in sequence. Finally, 3‐aminophenylboronic acid, as the functional monomer, was linked to the magnetic microspheres for capturing glycoprotein/glycopeptides. The results of this study indicate that phenylboronic acid functionalized magnetic microspheres show excellent adsorption performance toward glycoprotein/glycopeptides. The maximum absorbing capacity of the microspheres for fetuin was 108 mg/g, and the enrichment efficiency reached 89.7%, indicating their potential to separate and enrich glycoproteins from the complex biological samples.     

Efficient synthesis of ionic triblock copolyesters and facile access to charge‐reversal hybrid micelles

Novel carboxyl‐ and amino‐functionalized copolyesters, based on poly(ε‐caprolactone)‐block‐poly(butylene fumarate)‐block‐poly(ε‐caprolactone), were efficiently synthesized via Michael‐type thiol‐ene click chemistry. The resulting amphiphilic copolyesters with controllable molecular weights and abundant positively or negatively charged groups could spontaneously form pH‐sensitive micelles in aqueous solutions, as confirmed by transmission electron microscopy, dynamic light scattering, fluorescence probing technique, and zeta potential analyses. Importantly, charge‐reversal hybrid micelles can be obtained by co‐assembly of carboxyl‐ and amino‐functionalized copolyesters. The surface charges of hybrid micelles reversed rapidly from negative to positive at isoelectric point via protonation of surface carboxyl and amino groups. Interestingly, the hybrid micelles showed apparent pH‐triggered Nile red‐release behavior in acidic condition resembling tumor intracellular environment, which is fairly desirable for drug delivery. Our work indicates that co‐assembly is a facile but efficient way to prepare charge‐reversal micelles, which have great potential to be used as intelligent drug delivery systems for cancer therapy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1259–1267     

Thymine‐functionalized polystyrenes for applications in biotechnology. III. Increasing the thymine loading via a new synthetic pathway

In this article, we report an efficient method for the synthesis of thymine‐functionalized polystyrene microspheres. First, poly(styrene‐co‐4‐chloromethylstyrene) copolymers slightly crosslinked with divinylbenzene were synthesized in batch free‐radical emulsion copolymerization. Microspheres with a particle size of ～40–70 nm were obtained with greater than 99% conversion. The chloromethylstyrene (CMS) groups were then converted into thymylmethylstyrene (TMS) in a two‐phase system with greater than 80% efficiency, and up to a 45 mol % thymine loading was achieved. The functionalized microspheres were characterized by elemental analysis, Fourier transform infrared, and X‐ray photoelectron spectroscopy. The analyses revealed partial hydrolysis of the CMS functionalities, yielding hydroxymethyl functional groups in addition to the thymine functionalities. These copolymers have potential applications in biotechnology. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5545–5553, 2005     

Grafting of amino functional monomer onto initiator-modified polystyrene particles

Polystyrene nanoparticles with grafted chains of an amino functionalized polymer were prepared by a two-step polymerization process. In the first step, the polystyrene seed particles were synthesized by the conventional batch emulsion polymerization using terpolymer HAS (hydroperoxide monomer, acrylic acid, and styrene) as a surface-active initiator. The surface of the obtained particles contains carboxyl groups, which are responsible for the latex stability, and residual undecomposed hydroperoxide groups. Therefore, in the second step, an amino functional monomer was grafted onto the hydroperoxide modified polystyrene particles by a "grafting from" approach. X-ray photoelectron spectroscopy, NMR, and scanning electron microscopy were used to examine the surface of the amino functionalized particles. The amount of incorporated amino groups onto the particles was determined by fluorescenometric titration. In general, the number of amino groups on the particle surface increased with the increase of the functional monomer content in the reaction mixture. The incorporation of the functional monomer was also confirmed by electrophoretic measurements. Final particles possess amphoteric character due to the presence of amino and carboxyl groups on the surface. Adsorption of human immunoglobulins G onto the amino functionalized particles was studied as a function of pH and ionic strength. The covalent binding of human IgG was performed using the glutaraldehyde preactivation method. The immunoreactivity of the latex-IgG complex was examined by the latex agglutination test.