Preparation of l‐phenylalanine‐imprinted solid‐phase extraction sorbent by Pickering emulsion polymerization and the selective enrichment of l‐phenylalanine from human urine

A novel l‐ phenylalanine molecularly imprinted solid‐phase extraction sorbent was synthesized by the combination of Pickering emulsion polymerization and ion‐pair dummy template imprinting. Compared to other polymerization methods, the molecularly imprinted polymers thus prepared exhibit a high specific surface, large pore diameter, and appropriate particle size. The key parameters for solid‐phase extraction were optimized, and the result indicated that the molecularly imprinted polymer thus prepared exhibits a good recovery of 98.9% for l‐ phenylalanine. Under the optimized conditions of the procedure, an analytical method for l‐ phenylalanine was well established. By comparing the performance of the molecularly imprinted polymer and a commercial reverse‐phase silica gel, the obtained molecularly imprinted polymer as an solid‐phase extraction sorbent is more suitable, exhibiting high precision (relative standard deviation 3.2%, n = 4) and a low limit of detection (60.0 ± 1.9 nmol·L^?1) for the isolation of l‐ phenylalanine. Based on these results, the combination of the Pickering emulsion polymerization and ion‐pair dummy template imprinting is effective for preparing selective solid‐phase extraction sorbents for the separation of amino acids and organic acids from complex biological samples.     

Surface‐initiated nitroxide‐mediated polymerization of sodium 4‐styrene sulfonate from latex particles

In this study, we report the use of a double‐headed dialkoxyamine trithiocarbonate ( I ) capable of acting as chain transfer agent via reversible addition‐fragmentation chain transfer polymerization or as initiator via nitroxide‐mediated polymerization. It is worth mentioning that I was revealed as an effective dual chain transfer agent in the synthesis of multiblock copolymers via bulk and emulsion processes. In this article, we report the employing of I in dispersed systems to obtain amphiphilic multiblock copolymers and latexes. In this case, a water soluble macroagent of PAA previously synthetized was used in disperse media using a mixture of methanol/water (70:30, w/w). Stable latexes were obtained via polymerization‐induced self‐assembly and surface‐initiated polymerization of SSNa from alkoxyamine‐functionalized latex PAA‐b‐PS‐b‐PAA was also obtained © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 437–444     

Sonication‐Aided Formation of Hollow Hybrid Nanoparticles as High‐Efficiency Absorbents for Dissolved Toluene in Water

A surfactant‐free emulsion polymerization process was developed to produce hollow hybrid nanoparticles (HHNP thereafter). Ultrasonication was found not only to help the generation of nanosized monomer droplets but also to generate surface active species through mediating the hydrolysis of the monomer, 3‐(methacryloyloxy) propyltrimethoxysilane (MPS), thus stabilizing the oil/water interface. The hollow structure was formed based on a soft template approach, where the partially hydrolyzed monomer served as emulsifier and polymerized at the interface to form a hybrid shell. These HHNPs were used to absorb dissolved toluene in water and it was found they could reduce the toluene level down to zero, a level hardly being achieved by other methods. Combined with their good colloidal stability in water, these HHNPs are very promising colloidal collectors for dissolved organic solvents, in order to generate high quality water from contaminated water.     

In Situ Generated Janus Fabrics for the Rapid and Efficient Separation of Oil from Oil‐in‐Water Emulsions

A cotton fabric was coated with a polymer that contains both poly(dimethyl siloxane) (PDMS) and poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA). When the repeat unit number of PDMS is about three‐fold that of PDMAEMA and the fabric is exposed to air, the fabric is superhydrophobic because PDMS in the coating covers the PDMAEMA chains. Upon contact with an oil‐in‐water emulsion, the water‐soluble PDMAEMA rises to the top and the side in contact with the emulsion becomes hydrophilic. The emerged PDMAEMA chains then cause the emulsion droplets to coagulate, and the aggregated oil fills the pores on the superhydrophobic side of the fabric. The oil‐impregnated side remains hydrophobic even upon prolonged contact with water. Thus, a Janus fabric is elegantly generated in situ and sustained. This easy‐to‐prepare Janus fabric rapidly and efficiently separates oil from emulsions and may find practical applications.     

RAFT‐mediated batch emulsion polymerization of styrene using poly[N‐(4‐vinylbenzyl)‐N,N‐dibutylamine hydrochloride] trithiocarbonate as both surfactant and macro‐RAFT agent

Poly[N‐(4‐vinylbenzyl)‐N,N‐dibutylamine hydrochloride] trithiocarbonate, which contains the reactive trithiocarbonate group and the appending surface‐active groups, is used as both surfactant and macromolecular reversible addition‐fragmentation chain transfer (macro‐RAFT) agent in batch emulsion polymerization of styrene. Under the conditions at high monomer content of ～20 wt % and with the molecular weight of the macro‐RAFT agent ranging from 4.0 to 15.0 kg/mol, well‐controlled batch emulsion RAFT polymerization initiated by the hydrophilic 2‐2′‐azobis(2‐methylpropionamidine) dihydrochloride is achieved. The polymerization leads to formation of nano‐sized colloids of the poly[N‐(4‐vinylbenzyl)‐N,N‐dibutylamine hydrochloride]‐b‐ polystyrene‐b‐poly[N‐(4‐vinylbenzyl)‐N,N‐dibutylamine hydrochloride] triblock copolymer. The colloids generally have core‐shell structure, in which the hydrophilic block forms the shell and the hydrophobic block forms the core. The molecular weight of the triblock copolymer linearly increases with increase in the monomer conversion, and the values are well‐consistent with the theoretical ones. The molecular weight polydispersity index of the triblock copolymer is below 1.2 at most cases of polymerization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Designing superhydrophobic surface based on fluoropolymer–silica nanocomposite via RAFT‐mediated polymerization‐induced self‐assembly

Superhydrophobic surfaces (SHS) find versatile applications as coatings due to their very high water‐repellency, self‐cleaning, and anti‐icing properties. This investigation describes the preparation of a SHS from surfactant‐free hybrid fluoropolymer latex. In this case, reversible addition‐fragmentation chain transfer (RAFT) polymerization was adopted to prepare a copolymer of 4‐vinyl pyridine (4VP) and vinyl triethoxysilane (VTES), where the pyridine units were quaternized to make the copolymer soluble in water. The copolymer was further used as a macro‐RAFT agent to polymerize 2,2,2‐trifluoroethyl methacrylate (TFEMA) in a surfactant‐free emulsion via polymerization‐induced self‐assembly (PISA). The macro‐RAFT agent contained a small amount of VTES as co‐monomer which was utilized to graft silica nanoparticles (SNPs) onto the P(TFEMA) spheres. The film prepared using the nanocomposite latex exhibited a nano‐structured surface as observed by SEM and AFM analyses. Surface modification of the film with fluorinated trichlorosilane produced an SHS with a water contact angle (WCA) of 151.5°. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 266–275     

High‐density extraction solvent‐based solvent de‐emulsification dispersive liquid–liquid microextraction combined with MEKC for detection of chlorophenols in water samples

For the first time, the high‐density solvent‐based solvent de‐emulsification dispersive liquid–liquid microextraction (HSD‐DLLME) was developed for the fast, simple, and efficient determination of chlorophenols in water samples followed by field‐enhanced sample injection with reverse migrating micelles in CE. The extraction of chlorophenols in the aqueous sample solution was performed in the presence of extraction solvent (chloroform) and dispersive solvent (acetone). A de‐emulsification solvent (ACN) was then injected into the aqueous solution to break up the emulsion, the obtained emulsion cleared into two phases quickly. The lower layer (chloroform) was collected and analyzed by field‐enhanced sample injection with reverse migrating micelles in CE. Several important parameters influencing the extraction efficiency of HSD‐DLLME such as the type and volume of extraction solvent, disperser solvent and de‐emulsification solvent, sample pH, extraction time as well as salting‐out effects were optimized. Under the optimized conditions, the proposed method provided a good linearity in the range of 0.02–4 μg/mL, low LODs (4 ng/mL), and good repeatability of the extractions (RSDs below 9.3%, n = 5). And enrichment factors for three phenols were 684, 797, and 233, respectively. This method was then utilized to analyze two real environmental samples from wastewater and tap water and obtained satisfactory results. The obtained results indicated that the developed method is an excellent alternative for the routine analysis in the environmental field.     

Fabrication of Highly Spherical Millimeter‐Sized Poly(amic acid) Capsules by Removing Non‐Volatile Solvent

Millimeter‐sized highly spherical poly(amic acid) (PAA) capsules were prepared by curing an emulsion containing non‐volatile N,N‐dimethylacetamide (DMAc). Although the sphericity of the capsules (>99%) obtained by the emulsion method was slightly lower than that of corresponding polystyrene capsules, their surface was smooth. The curing conditions to achieve the highest degree of sphericity require stabilization and deformation, which were governed by parameters, such as PAA concentration, the viscosity of the emulsion matrix, stirring speed, and temperature.     

An Emulsifier‐Free RAFT‐Mediated Process for the Efficient Synthesis of Cerium Oxide/Polymer Hybrid Latexes

Hybrid latexes based on cerium oxide nanoparticles are synthesized via an emulsifier‐free process of emulsion polymerization employing amphiphatic macro‐RAFT agents. Poly(butyl acrylate‐co‐acrylic acid) random oligomers of various compositions and chain lengths are first obtained by RAFT copolymerization in the presence of a trithiocarbonate as controlling agent. In a second step, the seeded emulsion copolymerization of styrene and methyl acrylate is carried out in the presence of nanoceria with macro‐RAFT agents adsorbed at their surface, resulting in a high incorporation efficiency of cerium oxide nanoparticles in the final hybrid latexes, as evidenced by cryo‐transmission electron microscopy.     

Preparation of macroporous hydrophobic materials filled with aligned porous hydrophilic domain via emulsion‐templated and unidirectional freezing technique

A new class of porous materials, having hydrophobic scaffold embedded with aligned porous hydrophilic domains, was in situ fabricated through combination of emulsion‐templated method and unidirectional freezing technique. A water‐in‐oil high internal phase emulsion (HIPE) was prepared with the mixture of styrene and divinylbenzene as continuous phase and a poly(vinyl alcohol) (PVA) aqueous solution as dispersed phase. After polymerization of the continuous phase and subsequently unidirectional freezing, the dispersed phase, a macroporous poly(styrene/divinylbenzene) embedded with an aligned PVA domain, was obtained. The effects of the polymerization temperature, PVA concentration, and freezing rate on these porous materials were investigated. It was found that the PVA domain size and the aligned channel size were dependent on the polymerization temperature, the PVA concentration, and freezing rate. The fabrication method in this work, combining of unidirectional freezing and emulsion template, not only allows to prepare hydrophobic–hydrophilic polyHIPEs having a sea island structure but also dramatically improves the stiffness and specific surface area of the resulting polyHIPEs. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis of polymeric core–shell particles using surface‐initiated living free‐radical polymerization

An easy and novel approach to the synthesis of functionalized nanostructured polymeric particles is reported. The surfactant‐free emulsion polymerization of methyl methacrylate in the presence of the crosslinking reagent 2‐ethyl‐2‐(hydroxy methyl)‐1,3‐propanediol trimethacrylate was used to in situ crosslink colloid micelles to produce stable, crosslinked polymeric particles (diameter size ～ 100–300 nm). A functionalized methacrylate monomer, 2‐methacryloxyethyl‐2′‐bromoisobutyrate, containing a dormant atom transfer radical polymerization (ATRP) living free‐radical initiator, which is termed an inimer (initiator/monomer), was added to the solution during the polymerization to functionalize the surface of the particles with ATRP initiator groups. The surface‐initiated ATRP of different monomers was then carried out to produce core–shell‐type polymeric nanostructures. This versatile technique can be easily employed for the design of a wide variety of polymeric shells surrounding a crosslinked core while keeping good control over the sizes of the nanostructures. The particles were characterized with scanning electron microscopy, transmission electron microscopy, optical microscopy, dynamic light scattering, and Raman spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1575–1584, 2007     

Self‐assembly of block copolymers with an alkoxysilane‐based core‐forming block: A comparison of synthetic approaches

Polymerization‐induced self‐assembly (PISA) has become the preferred method of preparing self‐assembled nano‐objects based on amphiphilic block copolymers. The PISA methodology has also been extended to the realization of colloidal nanocomposites, such as polymer–silica hybrid particles. In this work, we compare two methods to prepare nanoparticles based on self‐assembly of block copolymers bearing a core‐forming block with a reactive alkoxysilane moiety (3‐(trimethoxysilyl)propyl methacrylate, MPS), namely (i) RAFT emulsion polymerization using a hydrophilic macroRAFT agent and (ii) solution‐phase self‐assembly upon slow addition of a selective solvent. Emulsion polymerization under both ab initio and seeded conditions were studied, as well the use of different initiating systems. Effective and reproducible chain extension (and hence PISA) of MPS via thermally initiated RAFT emulsion polymerization was compromised due to the hydrolysis and polycondensation of MPS occurring under the reaction conditions employed. A more successful approach to block copolymer self‐assembly was achieved via polymerization in a good solvent for both blocks (1,4‐dioxane) followed by the slow addition of water, yielding spherical nanoparticles that increased in size as the length of the solvophobic block was increased. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 420–429     

Preparation of emulsion‐templated fluorinated polymers and their application in oil/water separation

A series of emulsion‐templated fluorinated polymers (polyHIPEs) were first synthesized with introducing 2‐(perfluorohexyl)ethyl methacrylate (PEM) to the external phase of water‐in‐styrene high internal phase emulsion (HIPE) templates. The morphology (i.e., void size and its distribution) of these porous materials could be tuned simply by changing PEM and/or surfactant amount. The synergistic effect between the surface chemistry and surface architecture allowed the polyHIPEs to possess hydrophobicity with a water contact angle of 151°. The superhydrophobicity and oleophilicity of the polyHIPEs, together with their highly open porous structure, make the material a very competitive candidate as a filtration material for oil/water separation in practice with the efficiency of separating dichloromethane from the oil/water mixture of 95%. Such oil/water separating capacity was maintained after 10 cycles of filtration of oil/water, indicating the cyclic usage of the polyHIPE is feasible. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1508–1515     

NMR Studies of Active‐Site Properties of Human Carbonic Anhydrase II by Using 15N‐Labeled 4‐Methylimidazole as a Local Probe and Histidine Hydrogen‐Bond Correlations

By using a combination of liquid and solid‐state NMR spectroscopy, ¹⁵N‐labeled 4‐methylimidazole (4‐MI) as a local probe of the environment has been studied: 1) in the polar, wet Freon CDF₃/CDF₂Cl down to 130 K, 2) in water at pH 12, and 3) in solid samples of the mutant H64A of human carbonic anhydrase II (HCA II). In the latter, the active‐site His64 residue is replaced by alanine; the catalytic activity is, however, rescued by the presence of 4‐MI. For the Freon solution, it is demonstrated that addition of water molecules not only catalyzes proton tautomerism but also lifts its quasidegeneracy. The possible hydrogen‐bond clusters formed and the mechanism of the tautomerism are discussed. Information about the imidazole hydrogen‐bond geometries is obtained by establishing a correlation between published ¹H and ¹⁵N chemical shifts of the imidazole rings of histidines in proteins. This correlation is useful to distinguish histidines embedded in the interior of proteins and those at the surface, embedded in water. Moreover, evidence is obtained that the hydrogen‐bond geometries of His64 in the active site of HCA II and of 4‐MI in H64A HCA II are similar. Finally, the degeneracy of the rapid tautomerism of the neutral imidazole ring His64 reported by Shimahara et al. (J. Biol. Chem.­ 2007 , 282, 9646) can be explained with a wet, polar, nonaqueous active‐site conformation in the inward conformation, similar to the properties of 4‐MI in the Freon solution. The biological implications for the enzyme mechanism are discussed.     

Synthesis of snowman‐like polymer‐silica asymmetric particles by combination of hydrolytic condensation process with γ‐ray radiation initiated seeded emulsion polymerization

We report on a facile route to synthesize snowman‐like asymmetric composite particles via γ‐ray initiated seeded emulsion polymerization after a hydrolytic condensation process on the surface of second monomer swollen poly(styrene‐divinylbenzene‐acrylic acid) seeds. Effects of the amounts and kinds of second monomer and inorganic precursor, different radiation polymerization conditions including dose rates and absorbed doses on the morphology of the obtained particles were investigated. The obtained asymmetric particles can serve as ideal solid surfactants to stabilize the water‐in‐oil emulsions, and soap‐free hierarchical materials were obtained by polymerization of monomers in water or oil phase. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 339–348     

Oligomer formation in the emulsifier‐free emulsion polymerization of styrene

The formation of oligomers in emulsifier‐free emulsion polymerization of styrene was characterized by means of gel permeation chromatography and surface tension measurements. GPC analysis showed incessant oligomer formation throughout the emulsion polymerization process. Oligomers spanned a molecular weight range of 200–1,500, have an M̄_w of 800–900, an M̄_n of 600–800 and a polydispersity index of 1.3. On average, the oligomers contain 4 to 6 styrene units. UV detection could not be utilized to acquire the weight ratio of oligomers to polymers without correction. Combination was the major mode of termination of free radicals in the aqueous phase, but disproportionation was not negligible: for every three‐combination reactions there was about 1 disproportionation. Surface tension measurements showed that oligomers minimized the surface tension of the latex at about 50 min reaction to only 30 mN/m. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1323–1336, 2000     

Efficient and Selective Carboligation with Whole‐Cell Biocatalysts in Pickering Emulsion

Pickering emulsions (PEs) are particle‐stabilized multiphase systems with promising features for synthetic applications. Described here is a novel, simplified set‐up employing catalytically active whole cells for simultaneous emulsion stabilization and synthetic reaction. In the stereoselective carboligation of benzaldehyde to (R)‐benzoin catalyzed by a benzaldehyde lyase in E. coli, the set‐up yielded maximum substrate conversion within very short time, while economizing material demand and waste. Formation and activity of freshly produced PEs were enhanced when the catalytic whole cells were covered with hydrophobic silicone prior to PE formation. Benchmarked against other easy‐to‐handle whole‐cell biocatalysts in pure organic solvent, neat substrate, an aqueous emulsion in substrate, and a micro‐aquatic system, respectively, the cell‐stabilized PE outperformed all other systems by far.     

High‐Internal‐Phase Pickering Emulsions Stabilized Solely by Peanut‐Protein‐Isolate Microgel Particles with Multiple Potential Applications

High‐internal‐phase Pickering emulsions have various applications in materials science. However, the biocompatibility and biodegradability of inorganic or synthetic stabilizers limit their applications. Herein, we describe high‐internal‐phase Pickering emulsions with 87 % edible oil or 88 % n‐hexane in water stabilized by peanut‐protein‐isolate microgel particles. These dispersed phase fractions are the highest in all known food‐grade Pickering emulsions. The protein‐based microgel particles are in different aggregate states depending on the pH value. The emulsions can be utilized for multiple potential applications simply by changing the internal‐phase composition. A substitute for partially hydrogenated vegetable oils is obtained when the internal phase is an edible oil. If the internal phase is n‐hexane, the emulsion can be used as a template to produce porous materials, which are advantageous for tissue engineering.     

Replacement of benzene with regulators for the catalyzed polymerization of 1,3‐butadiene to high cis‐1,4‐polybutadiene

The polymerization regulators mesitylene and 1,3,5‐trimethoxybenzene were investigated as suitable substitutes for benzene in the cobalt(II) octanoate/diethylaluminum chloride/water‐catalyzed polymerization of 1,3‐butadiene to high cis‐1,4‐polybutadiene. The propagation rates were reduced by 50% with the inclusion of 18 mM mesitylene or 0.17 mM trimethoxybenzene. Mesitylene was found to be an inefficient polymerization regulator because it reduced the propagation rate by a combination of regulation and destruction of the active catalyst complex. Not only did trimethoxybenzene reduce the propagation rate by effective regulation at low concentration, it also increased the percentage activity of cobalt to 200%, indicating that two polymer chains were propagating simultaneously from each active center. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2244–2255, 2001     

Synthesis of amphiphilic cationic copolymers poly[2‐(methacryloyloxy)ethyl trimethylammonium chloride‐co‐stearyl methacrylate] and their self‐assembly behavior in water and water‐ethanol mixtures

A series of amphiphilic cationic random copolymers, namely poly[2‐(methacryloyloxy)ethyl trimethylammonium chloride‐co‐stearyl methacrylate] or poly(MADQUAT‐co‐SMA), have been synthesized via conventional free‐radical copolymerization using 2,2′‐azobisisobutyronitrile (AIBN) as initiator and n‐dodecanethiol as chain transfer agent. The resultant products were then characterized by FT‐IR, ¹H NMR, MALDI‐TOF MS measurements. From the number‐average molecular weights of the copolymers, we can conclude that these copolymers have oligomeric structure with a limited number of hydrophilic and hydrophobic moieties in a short polymer chain. The reactivity ratios (r_MADQUAT = 0.83, r_SMA = 0.25) between the hydrophilic MADQUAT monomer and the hydrophobic SMA monomer were calculated by the Finemann and Ross method, which was based on the results of ¹H NMR analysis. The surface activity of the random copolymers was studied by the combination of surface tension and contact angle measurement, and the results indicated that these copolymers possess relatively high surface activity. The critical aggregation concentrations (cac) of the copolymers in aqueous solution were determined by fluorescence probe method as well as surface tension measurement. The different nanoparticles of poly(MADQUAT‐co‐SMA) copolymers formed in pure water or ethanol‐water mixture were proved by the particle size and size distribution in the measurement of dynamic light scattering (DLS). Furthermore, using transmission electron microscopy (TEM), we could observe various self‐assembly morphologies of these random copolymer. All these results show that the amphiphilic cationic random copolymers have a good self‐assembly behavior, even if they are ill‐defined copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4670–4684, 2009