Thermo‐responsive glycopolymer chains grafted onto honeycomb structured porous films via RAFT polymerization as a thermo‐dependent switcher for lectin Concanavalin a conjugation

Stable and surface‐modified films with regular porous arrays were created by crosslinking honeycomb structured porous films prepared via breath figures from poly(styrene‐co‐maleic anhydride). The formation of open or closed pores of the films was controlled by the addition of a polyion complex. Subsequent crosslinking of the films with 1,8‐diaminooctane led to films, which maintain their structure in solvents. In addition, excess amino functionality after crosslinking allowed the attachment of RAFT agent, 3‐benzylsulfanyl thiocarbonyl sulfanylpropionic acid, for the controlled surface polymerization of N‐isopropyl acrylamide (NIPAAm) and N‐acryloyl glucosamine (AGA). The attachment of thermo‐responsive glycopolymers onto the honeycomb structured porous films was confirmed using contact angle measurements and confocal fluorescence microscopy. Cleavage of surface anchored polymers via aminolysis revealed that the molecular weights of the surface grafted chains are significantly larger than the molecular weight of the chains generated in solution. The honeycomb structured porous films with their grafted PNIPAAm‐ran‐PAGA polymer chains showed selective recognition of Concanavalin A (ConA). Below the lower critical solution temperature (LCST) of the surface, the conjugation is switched off, while above the LCST the surface grafted glucose moieties bind strongly to ConA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3440–3455, 2010     

The influence of casting parameters on the surface morphology of PS‐b‐P4VP honeycomb films

The “breath figures” method provides an efficient and cost‐effective method to produce highly ordered honeycomb patterns in polymeric films at micrometer and sub‐micrometer dimensions. The size and regularity of the pores can be adjusted through a series of physical and chemical parameters. In this study, amphiphilic diblock copolymers, polystyrene‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) with different lengths of P4VP, were synthesized through Reversible Addition‐Fragmentation Chain Transfer polymerization. The honeycomb‐patterned films were prepared from these well‐defined polymers through the dynamic breath figures method. A series of physical parameters including solution concentration, flow rate, humidity of the flow, and the humidity of the casting environment, were delicately adjusted to systematically investigate their effects on the morphology of the films. These studies identified four key factors which were found to influence the formation of the pattern. No obvious effect was found on the pore size by changing the length of P4VP block. The result provides clear direction on the fabrication of PS‐b‐P4VP honeycomb‐patterned films and more broadly contributes a deeper understanding of the processes involved in the formation of honeycomb patterns. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3721–3732     

Polystyrene (1)/poly(butyl acrylate/amide type functional monomer) (2) two-stage emulsion polymers. Synthesis and thermomechanical properties of latex films

Polystyrene (PS) (1)/Poly (n-butyl acrylate (BA)/amide type functional monomer) (2) structured latex particles were prepared through emulsion polymerization varying the hydrophilicity of the functional monomer employed. The second-stage polymerization kinetics, the size and morphology of latex particles, and the location of the functional groups in the final latexes were studied, in order to relate them to the thermomechanical properties of films cast from these latexes. It has been shown that, as expected, increasing the hydrophobicity leads to a better homogeneity in the copolymer formed during the second-stage polymerization, while the more hydrophilic functional monomer partly homopolymerizes in a separate phase. However, the functionalization by all the monomers used in this work, prevents the PS seed particles to form a continuous skeleton (percolated network). Further heat treatments at 140°C do not lead to the formation of a continuous PS phase as for pure BA/pure PS two-stage particles. In addition, some thermally induced crosslinking effects are discussed in relation with the functional monomer location within the particles. © 1995 John Wiley & Sons, Inc.     

Comparison of RAFT‐derived poly(vinylpyrrolidone) verses poly(oligoethyleneglycol methacrylate) for the stabilization of glycosylated gold nanoparticles

Carbohydrates dictate many biological processes including infection by pathogens. Glycosylated polymers and nanomaterials which have increased affinity due to the cluster glycoside effect, are therefore useful tools to probe function, but also as prophylactic therapies or diagnostic tools. Here, the effect of polymer structure on the coating of gold nanoparticles is studied in the context of grafting density, buffer stability, and in a lectin binding assay. RAFT polymerization is used to generate poly(oligoethyleneglycol methacrylates) and poly(N‐vinylpyrrolidones) with a thiol end‐group for subsequent immobilization onto the gold. It is observed that poly(oligoethylene glycol methacrylates), despite being widely used particle coatings, lead to low grafting densities which in turn resulted in lower stability in biological buffers. A depression of the cloud point upon nanoparticle immobilization is also seen, which might compromise performance. In comparison poly(vinylpyrrolidones) resulted in stable particles with higher grafting densities due to the compact size of each monomer unit. The higher grafting density also enabled an increase in the number of carbohydrates which can be installed per nanoparticle at the chain ends, and gave increased binding in a lectin recognition assay. These results will guide the development of new nanoparticle biosensors with enhanced specificity, affinity, and stability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 55, 1200–1208     

Facile fabrication of porous pure and Ag nanoparticle-doped poly(4-vinylpyridine) films at the liquid-liquid interfaces

We reported an interfacial self-assembly of regularly layered porous poly(4-vinylpyridine)(P4VP) films at the interfaces of water-chloroform or -dichloroethane.The porous diameters were in the range from hundred nanometers to several micrometers.It was revealed that formation of such kind of porous materials was solvent dependent.Moreover,cyclic Ag nanoparticles could be grown in the porous P4VP films to form Ag-P4VP nanohybrids under radiation.     

Polystyrene(1)/poly(butyl acrylate-methacrylic acid)(2) core-shell emulsion polymers. Part II: Thermomechanical properties of latex films

Polystyrene(1)/poly(n-butyl acrylate-methacrylic acid)(2) structured latex particles were prepared through a two-stage emulsion polymerization procedure, using a polystyrene (PS) latex seed (118 nm), and differentn-butyl acrylate (BA)/methacrylic acid (MAA) ratios. Polymerization kinetics, particle morphology, and MAA location have already been discussed in the first part of this series. In this second part the thermomechanical behavior of films cast from these latexes was studied. Differential Thermal Analysis and Dynamic Mechanical Analysis (DMA) were employed as characterization techniques for the films. Two polymer phases corresponding to polystyrene and a poly(BA-MAA) copolymer were distinguished. Comparison was made to analogous unfunctionalized PS/PBA systems, as a result of which an effect of MAA upon the phase arrangement in the film was found. Scanning Electron Microscopy of film samples and DMA showed that the evolution of the phase arrangement as a result of annealing was strongly dependent on the type of mechanical and heat treatments being applied to functionalized systems. Finally, the thermomechanical behavior of films was related to the structural features of the corresponding latexes, and computer simulation techniques wer eemployed to establish a mechanistic support for these relationships.     

Synthesis of bis(2,2′:6′,2″-terpyridine)-terminated telechelic polymers by RAFT polymerization and ruthenium-polymer complexation thereof

Well-defined polystyrenes and poly(n-butyl acrylate)s of the two ends being functionalized with terpyridine groups were synthesized via addition-fragmentation chain transfer (RAFT) polymerization using a symmetric bisterpyridine-functionalized trithiocarbonate as a chain transfer agent (CTA). Kinetic studies on RAFT mediated thermal polymerization of styrene indicated the controlled polymerization. Corresponding triblock copolymers of styrene and n-butyl acrylate were obtained by utilizing the bisterpyridine-functionalized homopolymers as the macro-CTAs. Supramolecular metallo-polystyrenes with different repeat blocks were prepared by the chelating interaction between the terpyridine ends and Ru(II) ions. The formation of the metallo-polymers was proven by UV-vis spectra and dynamic light scattering (DLS).     

Synthesis of degradable poly(methyl methacrylate) star polymers via RAFT copolymerization with cyclic ketene acetals

Copolymerization of the cyclic ketene acetal 5,6‐benzo‐2‐methylene‐1,3‐dioxepane (BMDO) with methyl methacrylate (MMA) is studied with respect to its copolymerization parameters and the suitability to control BMDO/MMA copolymerizations via the reversible addition‐fragmentation chain transfer (RAFT) technique to obtain linear and 4‐arm star polymers. BMDO shows disparate copolymerization behavior with MMA and r₁ = 0.33 ± 0.06 and r₂ = 6.0 ± 0.8 have been determined for polymerization at 110 °C in anisole from fitting copolymer composition vs. comonomer feed data to the Lewis–Mayo equation. Copolymerization of the two monomers is successful in RAFT polymerization employing a trithiocarbonate control agent. As desired, polymers contain only little amount of polyester units stemming from BMDO units and preliminary degradation experiment show that the polymer degrades slowly, but steadily in aqueous 1 M NaOH dispersion. Within ten days, the polymers are broken down to low molecular weight segments from an initial molecular weight of M_n = 6000 g mol^?1. Star (co)polymerization with an erythritol‐based tetra‐functional RAFT agent following the Z‐group approach proceeds efficiently and polymers with a number‐average molecular weight of 10,000 g mol^?1 are readily obtained that degrade in similar manner as the linear copolymer counterparts. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1633–1641     

Synthesis of transparent block copolymers consisting of poly(diisopropyl fumarate) and poly(2-ethylhexyl acrylate) segments by reversible addition-fragmentation chain transfer polymerization using trithiocarbonates as the chain transfer agents

The reversible addition-fragmentation chain transfer polymerization of diisopropyl fumarate (DiPF) was carried out using ethyl 2-[[(dodecylthio)thioxymethyl]thio]-2-methylpropionate (T1) and 1,1′-(1,2-ethanediyl) bis[2-[[(dodecylthio)thioxymethyl]thio]-2-methylpropionate] (T2) as the monofunctional and difunctional chain transfer agents (CTAs) to synthesize poly(diisopropyl fumarate) (PDiPF) with a rigid chain conformation. The obtained PDiPF had a well-controlled molecular weight, molecular weight distribution, and structure of the chain ends. Size exclusion chromatography and NMR measurements revealed an excellent introduction efficiency (84–98%) of the terminal trithiocarbonate group into the polymer chain end. They were available as the monofunctional and difunctional macro-CTAs to synthesize the AB and ABA block copolymers, respectively. While the well-controlled block copolymers were solely obtained by the polymerization of 2-ethylhexyl acrylate as the second monomer in the presence of PDiPF as the macro-CTA, the block copolymerization of DiPF using poly(2-ethylhexyl acrylate) as the macro-CTA failed. The trithiocarbonate group at the chain end was completely removed by the reaction with n-butylamine and it was valid for the improvement of the coloration and other optical properties of the transparent polymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2584–2594     

Power‐law scaling of structured poly(p‐xylylene) films deposited by oblique angle

This study describes the evolution and growth of structured polymers by oblique angle deposition of poly(p‐xylylene) (PPX) derivatives. The deposition of structured PPX polymers have been demonstrated recently, but the mechanism of growth has not been studied. Here, we provide experimental evidence for the growth of structured PPX polymers by an atomic force microscope, electron microscope, and a profilometer. Individual columns expand with respect to their heights according to a power‐law, d = ch^p, where d is the column diameter, c and p are constants, and h is the height of a column. Values of p for structured poly(chloro‐p‐xylylene), poly(trifloroacetly‐p‐xylylene‐co‐p‐xylylene), and poly(bromo‐p‐xylylene) films are estimated as 0.11 ± 0.01, 0.15 ± 0.01, and 0.18 ± 0.01, respectively. This result is different from the traditional oblique angle deposition processes of nonpolymeric materials where the surface diffusion is low. Further analysis with two‐dimensional power spectral density (PSD) method showed that the ordering of columns is quasi‐periodic. Additionally, the X‐ray and transmission electron microscope characterization of the columns revealed that the columns are semicrystalline. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 640–648, 2008     

Photopatternable substrate‐independent poly(glycidyl methacrylate‐ran‐2‐(acryloyloxy) ethyl 2‐methylacrylate) polymer films for immobilization of biomolecules

We report the synthesis and characterization of a photocrosslinkable copolymer containing reactive epoxy groups for binding biomolecules. The epoxide‐containing copolymer poly(glycidyl methacrylate‐ran‐2‐(acryloyloxy) ethyl 2‐methylacrylate) offers distinct advantages such as ease of application to various substrates, enhanced stability of the bound oligonucleotide, low autofluorescence, and the ability to be photopatterned allowing localization of the linkers. The copolymer uses pendant acryloyl groups to control the crosslinking without sacrificing the epoxide groups. The films were characterized using ellipsometry, atomic force microscopy, and fluorescence microscopy. The films on glass, silicon wafer, and stainless steel showed no appreciable degradation in water, tetrahydrofuran, and acetone for ～4 months. The surface topography for a given thickness of crosslinked film was dictated by the deposition conditions. A 16mer oligonucleotide was immobilized on the thin films. A linear relationship between the film thickness and amount of oligonucleotide immobilized was observed with a maximum signal‐to‐background ratio (S/B) of 225 for a 60‐nm‐thick film, a value 50% higher than the S/B for an epoxide monolayer. The crosslinked films maintained a high fluorescence signal following long aqueous washing which is appealing for biological microarrays, immobilizing proteins, and study of slow differentiating cells where stability of the scaffold is relevant. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5826–5838, 2008     

Ab initio RAFT emulsion polymerization of butadiene using the amphiphilic poly(acrylic acid‐b‐styrene) trithiocarbonate as both surfactant and mediator

Ab initio reversible addition fragmentation chain transfer (RAFT) emulsion polymerization of butadiene was investigated by using the amphiphilic poly(acrylic acid_n‐b‐styrene₅) trithiocarbonate as both surfactant and mediator. The neutralization on acrylic acid (AA) units played significant influence on the gelation. When half of the AA units were neutralized, the gelation occurred in the early stage of the polymerization so that the highest accessible molecular weight of polybutadiene was as low as 5 kg mol^?1. In the non‐neutralized conditions, the gelation was much retarded so that the highest accessible molecular weight was increased up to 23 kg mol^?1. In the non‐neutralized conditions, potassium persulfate could not initiate the polymerization. When azobisisobutyronitrile was used as initiator, the polymerization mediated by poly(acrylic acid₂₇‐b‐styrene₅) trithiocarbonate could proceed much faster than the solution polymerization did. The latex was stable. Before the gel point, molecular weight agreed well with the theoretical prediction while PDI was relatively high due to the branching reaction. The poly(butadiene‐b‐styrene) core/shell particles could obtained by extending polybutadiene. When the n value in poly (acrylic acid_n‐b‐styrene₅) trithiocarbonate was lower than 20, the coalescence would occur, leading to the formation of some coagulum. On the other hand, when n value was as high as 60, the molecular weight was out of control. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Core‐shell microspheres with surface grafted poly(vinyl alcohol) as drug carriers for the treatment of hepatocellular carcinoma

Core(polyvinyl neodecanoate‐ethylene glycol dimethacrylate)‐shell(polyvinyl alcohol) (core (P(VND‐EGDMA))‐shell(PVA)) microspheres were developed by seeded polymerization with the use of conventional free radical and RAFT/MADIX mediated polymerization. Poly(vinyl pivalate) PVPi was grafted onto microspheres prepared via suspension polymerization of vinylneodecanoate and ethylene glycol dimethacrylate. The amount of grafted polymer was found to be independent from the technique used with conventional free radical polymerization and MADIX polymerization resulting into similar shell thicknesses. Both systems—grafting via free radical polymerization or the MADIX process—were found to follow slightly different kinetics. While the free radical polymerization resulted in a weight gain linear with the monomer consumption in solution the growth in the MADIX controlled system experienced a delay. The core‐shell microspheres were obtained by hydrolysis of the poly(vinyl pivalate) surface grafted brushes to form poly(vinyl alcohol). During hydrolysis the microspheres lost a significant amount of weight, consistent with the hydrolysis of 40–70% of all VPi units. Drug loading was found to be independent of the shell layer thickness, suggesting that the drug loading is governed by the amount of bulk material. The shell layer does not appear to represent an obstacle to the drug ingress. Cell testing using colorectal cancer cell lines HT 29 confirm the biocompatibility of the empty microspheres whereas the clofazimine loaded particles lead to 50% cell death, confirming the release of the drug. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3256–3272, 2007     

Cross-linked poly(2-hydroxyethylmethacrylate) films doped with 1,2-diaminoanthraquinone (DAQ) as efficient materials for the colorimetric sensing of nitric oxide and nitrite anion

A series of cross-linked poly(2-hydroxyethylmethacrylate) (polyHEMA) films doped with 1,2-diaminoanthraquinone (DAQ) are described. The synthesis of the DAQ-containing polymers does not require any previous derivatization of the diamine. The films can be used as solid-state colorimetric sensors for nitrite anion as well as for aqueous and gaseous nitric oxide. Polymers show no appreciable leaching of DAQ even after six months of storage in water.     

Construction of hydroxyl‐terminated poly(N‐isopropylacrylamide) brushes on silicon wafer via surface‐initiated atom transfer radical polymerization

Surface‐initiated atom transfer radical polymerization (SI‐ATRP) of N‐isopropylacrylamide (NIPAM) on silicon wafer in the presence of 2‐mercaptoethanol (ME) chain transfer agent was conducted in attempt to create controllable hydroxyl‐terminated brushes. The initiator‐immobilized substrate, was prepared by the esterification of hydroxyl groups on silicon wafer with 2‐bromopropionyl bromide (2‐BPB); followed by the ATRP of NIPAM using a catalyst system, that is, Cu(I)Br/2,2′‐bipyridine (2,2′‐bpy) and a chain transfer agent, that is, ME. The formation of homogeneous tethered poly(N‐isopropylacrylamide) (poly(NIPAM) brushes with hydroxyl end‐group, whose thickness can be tuned by chancing ME concentration, is evidenced by using the combination of grazing angle attenuated total reflectance‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, ellipsometry, atomic force microscopy, gel permeation chromatography, and water contact‐angle measurements. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(NIPAM) films with hydroxyl end‐group on silicon wafer and allowed us to predict a ME concentration for forming a “brush” conformation for the chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3880–3887, 2010     

Poly(caprolactone triol) as plasticizer agent for cellulose acetate films: influence of the preparation procedure and plasticizer content on the physico‐chemical properties

The influence of the plasticizer content and film preparation procedure on the morphology, density, thermal and mechanical properties of cellulose acetate (CA) films plasticized with poly‐(caprolactone triol) (PCL‐T), were studied. Differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), scanning electron microscopy (SEM), wide‐angle X‐ray diffraction (WAXD) and infrared spectroscopy (FT‐IR) techniques were used. The films were prepared by dry‐casting CA and CA/PCL‐T in acetone or acetone/water solutions, which produced transparent and opaque films, respectively. In contrast to the transparent films, which were dense, the opaque films presented a porous morphology. However, the presence of PCL‐T reduced the opaque film porosity, increasing, in consequence, its bulk density. The TMA results revealed that PCL‐T reduced the glass transition temperature more significantly in the transparent than in opaque films. Only the transparent CA/PCL‐T films presented a melting temperature, that reduced with higher concentrations of PCL‐T, suggesting a higher ordering (crystallinity) when the films were prepared in the absence of water, as observed from WAXD curves. The mechanical properties also showed that the transparent films were more soft and tough than the opaque films. In summary, PCL‐T was a good plasticizer agent for CA films due to the presence of hydrogen bonds between the components (FT‐IR spectra). The presence of water in the dry casting process has a significant effect mainly on film morphology and mechanical properties. Copyright © 2004 John Wiley & Sons, Ltd.     

On the preparation of stable poly(2-hydroxyethyl methacrylate) nanoparticles

A comprehensive experimental study of aqueous heterophase homopolymerization of 2-hydroxyetyl methacrylate revealed special conditions that must be fulfilled in order to obtain stable latex particles in the nanometer size range. The results clearly show that the formation and the stability of this kind of hydrophilic latex particle strongly depends on the hydrophobic-hydrophilic properties of both the initiating radicals and the stabilizers. Hydrophobic initiators in combination with sodium alkyl sulfate surfactants of proper chain lengths or ionic surface-active initiators lead to stable latex particles. In the latter case the particles keep their identity and spherical shape even after drying of the aqueous dispersion.     

Thianthrene as an activating group for the synthesis of poly(aryl ether thianthrene)s by nucleophilic aromatic substitution

A method for the preparation of poly(aryl ether thianthrene)s has been developed in which the aryl ether linkage is generated in the polymer‐forming reaction. The thianthrene heterocycle is sufficiently electron‐withdrawing to allow fluoro displacement with phenoxides by nucleophilic aromatic substitution. The monomer for this reaction, 2,7‐difluorothianthrene, can be synthesized in a moderate yield by a simple reaction sequence. Semiempirical calculations at the PM3 level suggest that 2,7‐difluorothianthrene is sufficiently activated, whereas NMR spectroscopy (¹H and ¹³C) indicates that the monomer is only slightly activated or (¹⁹F) not sufficiently activated for nucleophilic aromatic substitution. Model reactions with p‐cresol have demonstrated that the fluorine atoms on 2,7‐difluorothianthrene are readily displaced by phenoxides in high yields, and the process has been deemed suitable for polymer‐forming reactions. High‐molecular‐weight polymers have been produced from bisphenol A, bisphenol AF, and 4,4′‐biphenol. The polymers have been characterized with gel permeation chromatography, NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The glass‐transition temperatures for the polymers of different compositions and molecular weights range from 138 to 181 °C, and all the polymers have shown high thermooxidative stability, with 5% weight loss values in an air environment approaching 500 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6353–6363, 2004     

Synthesis of fac‐Ir(ppy)3 end‐functionalized poly(1,3‐cyclohexadiene): single monomer addition of fac‐Ir(ppy)2(vppy) for well‐controlled polymer synthesis

Synthesis of the polymer whose end is functionalized by fac‐Ir(ppy)₃ (ppy = 2‐phenylpyridyl) was achieved by using (living) anionic polymerization of 1,3‐cyclohexadiene: the reaction of poly(1,3‐cyclohexadienyl)lithium (PCHDLi) with fac‐Ir(ppy)₂(vppy) [vppy = 2‐(4‐vinylphenyl)pyridyl] resulted in nucleophilic attack of the carbanion in PCHDLi on the vinyl group of fac‐Ir(ppy)₂(vppy) selectively. Complexation of the pyridyl ring protected the α‐carbons of fac‐Ir(ppy)₂(vppy) from the reaction of the anionic polymer. The homopolymerization of fac‐Ir(ppy)₂(vppy) did not occur, and only one molecule of fac‐Ir(ppy)₂(vppy) reacted with the carbanion of PCHDLi and was selectively incorporated into an end of poly(1,3‐cyclohexadiene) (PCHD). Thus, the PCHD with fac‐Ir(ppy)₃ end‐group was obtained with a well‐controlled and defined polymer structure and molecular weight. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012