Synthesis of Film-Forming Photoactive Latex Particles by Emulsion Polymerization-Induced Self-Assembly to Produce Singlet Oxygen.

The design of photoactive polymer substrates producing singlet oxygen under visible light irradiation has great technological potential. Aqueous dispersion of novel photoactive core-shell particles was synthesized by surfactant-free reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of n-butyl acrylate. The surface of the nanoparticles is directly decorated thanks to the polymerization-induced self-assembly process using a hydrophilic macromolecular chain transfer agent (macro-CTA) functionalized with the organic photosensitizer. The macro-CTA was synthesized by statistical copolymerization of acrylic acid and 2-Rose Bengal ethyl acrylate (RBEA) at 80 °C mediated with 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid. Monitoring polymerization kinetics of RAFT polymerization highlights that increasing amount of RBEA induces retardation, still more pronounced when using the vinylbenzyl Rose Bengal comonomer. The present work provides insight into the quantum yield of singlet oxygen production in water (ΦΔ  = 0.2-0.6) for the three types of synthesized polymers (hydrophilic polymer, latex particles, and polymer film). The photoactive core-shell latex particles enabled the easy preparation of photoactive polymer film by simple casting.

Polymer Nanospheres with Hydrophobic Surface Groups as Supramolecular Building Blocks Produced by Aqueous PISA.

A robust and straightforward synthesis of waterborne polymer nanospheres bearing the supramolecular association unit dialkoxynapthalene at their surface is presented using polymerization-induced self-assembly (PISA). A RAFT agent bearing this unit is first employed to produce poly(acrylic acid) chains, which are then chain-extended with styrene (S) to spontaneously form the nano-objects via RAFT aqueous emulsion polymerization. The particular challenge posed by the dialkoxynapthalene hydrophobicity can be overcome by the use of PISA and the deprotonation of the poly(acrylic acid). At pH = 7, very homogeneous latexes are obtained. The particle diameters can be tuned from 36 to 105 nm (with a narrow particle size distribution) by varying the molar mass of the PS block. The surface accessibility of the dialkoxynapthalene moieties is demonstrated by complexation with the complementary host cyclobis(paraquat-p-phenylene) (CBPQT4+ · Cl- ), highlighting the potential of the nanospheres to act as building blocks for responsive supramolecular structures.

Deproteinised natural rubber latex grafted poly(dimethylaminoethyl methacrylate) - poly(vinyl alcohol) blend membranes: Synthesis, properties and application.

Natural rubber latex was initially deproteinised (DNRL) and then subjected to physicochemical modifications to make high functional membranes for drug delivery applications. Initially, DNRL was prepared by incubating with urea, sodiumdodecylsulphate and acetone followed by centrifugation. The deproteinisation was confirmed by CHN analysis. The DNRL was then chemically modified by grafting (dimethylaminoethyl methacrylate) onto NR particles by using a redox initiator system viz; cumene hydroperoxide/tetraethylenepentamine, followed by dialysis for purification. The grafting was confirmed by dynamic light scattering, Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The grafted system was blended with a hydrophilic adhesive polymer PVA and casted into membranes. The membranes after blending showed enhanced mechanical properties with a threshold concentration of PVA. The moisture uptake, swelling and water contact angle experiments indicated an increased hydrophilicity with an increased PVA content in the blend membranes. The grafted DNRL possessed significant antibacterial property which has been found to be retained in the blended form. A notable decrease in cytotoxicity was observed for the modified DNRL membranes than the bare DNRL membranes. The in-vitro drug release studies using rhodamine B as a model drug, confirmed the utility of the prepared membranes to function as a drug delivery matrix.

Facile Fabrication of Water Dispersible Latex Particles with Homogeneous or Chain-Segregated Surface from RAFT Polymerization Using a Mixture of Two Macromolecular Chain Transfer Agents.

Water dispersible latex particles with randomly mixed shells or chain segregated surface are synthesized from one-pot reversible addition-fragmentation chain transfer heterogeneous polymerization of benzyl methacrylate (BzMA) using a mixture of poly(glycerol monomethacrylate) (PGMA) and poly(2,3-bis(succinyloxy)propyl methacrylate) (PBSPMA) macromolecular chain transfer agents. In methanol, the two in situ synthesized PGMA-b-PBzMA and PBSPMA-b-PBzMA diblock copolymers coaggregate into spherical micelles, which contain PBzMA core and discrete PGMA and PBSPMA nanodomains on the shell. In contrast, in water-methanol mixture (V/V = 9/1), latex particles with homogeneous distribution of PGMA and PBSPMA polymer chains on the shell are obtained. The reasons leading to formation of latex particles with homogenous or chain-segregated surface are discussed, and polymerization kinetics and physical state of PBSPMA in methanol and water-methanol mixtures are ascribed. These polymeric micelles with patterned functional group on the surface are potentially important for application in supracolloidal hierarchical assemblies and catalysis.

Comparison of Loading Efficiency between Hyperbranched Polymers and Cross-Linked Nanogels at Various Branching Densities.

The effect of branching point structures and densities is studied between azido-containing hyperbranched polymers and cross-linked nanogels on their loading efficiency of alkynyl-containing dendron molecules. Hyperbranched polymers that contained "T"-shaped branching linkage from which three chains radiated out and cross-linked nanogels that contained "X"-shaped branching linkage with four radiating chains are synthesized in microemulsion using either atom transfer radical polymerization (ATRP) or conventional radical polymerization (RP) technique. Both polymers have similar density of azido groups in the structure and exhibit similar hydrodynamic diameter in latexes before purification. Subsequent copper-catalyzed azide-alkyne cycloaddition reactions between these polymers and alkynyl-containing dendrons in various sizes (G1-G3) demonstrate an order of dendron loading efficiencies (i.e., final conversion of alkynyl-containing dendron) as hyperbranched polymers > nanogels synthesized by ATRP > nanogels synthesized by RP. Decreasing the branching density or using smaller dendron molecules increases the click efficiency of both polymers. When G2 dendrons with a molecular weight of 627 Da are used to click with the hyperbranched polymers composed of 100% inimer, a maximum loading efficiency of G2 in the loaded hyperbranched polymer is 58% of G2 by weight. These results represent the first comparison between hyperbranched polymers and cross-linked nanogels to explore the effect of branching structures on their loading efficiencies.

Temperature triggered shape memory effect of transpolyisoprene-based polymer.

INTRODUCTION: Pure gutta-percha (trans-1, 4-polyisoprene [TPI]) has been used extensively as a main component of gutta-percha for root canal filling. TPI has the interesting shape memory property by cross-linking, and this polymer was commercialized under the product name of SMP-2 (Kuraray Corp, Kashima, Japan). Therefore, the purpose of this study was to examine the thermal properties and the mechanism of the shape memory function of cross-linked SMP-2. METHODS: The crystalline of the TPI was observed by x-ray diffraction. The effects of temperature on shape recovery, recovery stress, and relaxation modulus (Er[5]) were measured in cross-linked cylindrical specimens of SMP-2. Differential scanning calorimetry was used to monitor thermal events. RESULTS: On heating, a pronounced increase in recovery stress, a marked decrease in Er(5), and endothermic DSC peaks were observed over the same temperature range (38°-51°C) with shape recovery. On the other hand, on cooling, a pronounced decrease in recovery stress, a marked increase in Er(5), and an exothermic DSC peak were observed over the same temperature range (27°-33°C). CONCLUSIONS: The shape memory property of TPI is derived from its crystallinity and cross-linking ability. Fixing the deformed shape and shape recovery from the deformed shape to the original shape is relatively easy to achieve by changing the temperature of SMP-2. The shape memory function of the cross-linked SMP-2 was expected to be very useful as a root canal filling material by the modification of its some thermal properties.

Uranium(IV) amido-borohydrides as highly active diene polymerisation catalysts.

The synthesis and structural characterisation of the uranium(IV) amido-borohydrides (N'')2U{κ(2)-N(SiMe3)SiMe2CH2BBN-H} and U{κ(2)-N(SiMe3)SiMe2CH2BBN-H}2, and their activity as pre-catalysts for the polymerisation of isoprene are described.

Synthesis and characterization of novel polyacid-stabilized latexes.

A series of novel polyacid macromonomers based on 2-hydroxypropyl methacrylate (HPMA) were prepared by atom transfer radical polymerization (ATRP) via a two-step route. First, a range of well-defined PHPMA homopolymer precursors were synthesized by ATRP using a tertiary amine-functionalized initiator, 2-(dimethylamino)ethyl-2-bromoisobutyrylamide, and a CuCl/2, 2'-bipyridine (bpy) catalyst in alcoholic media at 50 °C. ATRP polymerizations were relatively slow and poorly controlled in pure isopropanol (IPA), especially when targeting higher degrees of polymerization (DP > 30). Improved control was achieved by addition of water: low polydispersity (M(w)/M(n) < 1.25) PHPMA homopolymers of DP = 30, 40, 50, 60, or 70 were successfully prepared using a 9:1 w/w % IPA/water mixture at 50 °C. These PHPMA homopolymer precursors were then derivatized to produce the corresponding poly(2-(succinyloxy)propyl methacrylate) (PSPMA) macromonomers by quaternizing the tertiary amine end-group with excess 4-vinylbenzyl chloride, followed by esterification of the pendent hydroxyl groups using excess succinic anhydride at 20 °C. These polyacid macromonomers were evaluated as reactive steric stabilizers for polystyrene latex synthesis under either aqueous emulsion polymerization or alcoholic dispersion polymerization conditions. Near-monodisperse polystyrene latexes were obtained via aqueous emulsion polymerization using 10 wt % PSPMA macromonomer (with respect to styrene monomer) with various initiators as evidenced by scanning electron microscopy, disk centrifuge photosedimentometry and light scattering studies. PSPMA macromomer concentrations as low as 1.0 wt % also produced near-monodisperse latexes, suggesting that these PSPMA macromonomers are highly effective stabilizers. Alcoholic dispersion polymerization of styrene conducted in various ethanol/water mixtures with 10 wt % PSPMA(50) macromonomer produced relatively large near-monodisperse latexes. Increasing the water content in such formulations led to smaller latexes, as expected. Control experiments conducted with 10 wt % PSPMA(50) homopolymer produced relatively large polydisperse latexes via emulsion polymerization and only macroscopic precipitates via alcoholic dispersion polymerization. Thus the terminal styrene group on the macromonomer chains is essential for the formation of well-defined latexes. FT-IR spectroscopy indicated that these latexes contained PSPMA macromonomer, whereas (1)H NMR spectroscopy studies of dissolved latexes allowed stabilizer contents to be determined. Aqueous electrophoresis and X-ray photoelectron spectroscopy studies confirmed that the PSPMA macromonomer chains were located at the latex surface, as expected. Finally, these polyacid-stabilized polystyrene latexes exhibited excellent freeze-thaw stability and remained colloidally stable in the presence of electrolyte.

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.

Adsorption of sterically stabilized latex particles at liquid surfaces: effects of steric stabilizer surface coverage, particle size, and chain length on particle wettability.

A series of five near-monodisperse sterically stabilized polystyrene (PS) latexes were synthesized using three well-defined poly(glycerol monomethacrylate) (PGMA) macromonomers with mean degrees of polymerization (DP) of 30, 50, or 70. The surface coverage and grafting density of the PGMA chains on the particle surface were determined using XPS and (1)H NMR spectroscopy, respectively. The wettability of individual latex particles adsorbed at the air-water and n-dodecane-water interfaces was studied using both the gel trapping technique and the film calliper method. The particle equilibrium contact angle at both interfaces is relatively insensitive to the mean DP of the PGMA stabilizer chains. For a fixed stabilizer DP of 30, particle contact angles were only weakly dependent on the particle size. The results are consistent with a model of compact hydrated layers of PGMA stabilizer chains at the particle surface over a wide range of grafting densities. Our approach could be utilized for studying the adsorption behavior of a broader range of sterically stabilized inorganic and polymeric particles of practical importance.

Synthesis of polyisoprene terpenoid dendrons and their applications in oligo(phenylene ethynylene)s as "shells".

The novel double-stage convergent synthesis of a new class of polyisoprene terpenoid (PIPTP) dendrons is described. PIPTP dendrons bear a highly branched aliphatic hydrocarbon skeleton and a hydrophilic hydroxy focal point functionality. These dendrons have the specific formula C((5×2)(G+1)(-5))H((5×2)(G+2)(-8))O, and each dendritic layer is constructed from an isoprene unit. The key branching steps involve a double alkyl-metal addition to an ester functionality, followed by deoxygenation of the resulting tertiary alcohol by triethylsilane and trifluoroacetic acid, then hydrogenation or hydrogenolysis. The dendrons were also attached to oligo(phenylene ethynylene)s (OPEs) so as to function as protective shells to allow fine tuning of the nanoscopic environment around the OPE moiety, and to exert precise control of the packing density and intermolecular interaction between the OPE cores. Fluorescence quantum yield data reveal that the OPE core is better encapsulated by the PIPTP dendrons than by Fréchet dendrons.

Liquid marbles prepared from pH-responsive sterically stabilized latex particles.

Submicrometer-sized pH-responsive sterically stabilized polystyrene (PS) latex particles were synthesized by dispersion polymerization in isopropyl alcohol with a poly[2-(diethylamino)ethyl methacrylate]- (PDEA-) based macroinitiator. These PDEA-PS latexes were extensively characterized with respect to their particle size distribution, morphology, chemical composition, and pH-responsive behavior. Millimeter- and centimeter-sized "liquid marbles" with aqueous volumes varying between 15 µL and 2.0 mL were readily prepared by rolling water droplets on the dried PDEA-PS latex powder. The larger liquid marbles adopted nonspherical shapes due to gravitational forces; analysis of this deformation enabled the surface tension to be estimated. Scanning electron microscopy and fluorescence microscopy studies indicated that flocs of the PDEA-PS particles were adsorbed at the surface of these water droplets, leading to stable liquid marbles. The relative mechanical integrity of the liquid marbles prepared from alkaline aqueous solution (pH 10) was higher than those prepared from acidic aqueous solution (pH 2) as judged by droplet roller experiments. These liquid marbles exhibited long-term stability (over 1 h) when transferred onto the surface of liquid water, provided that the solution pH of the subphase was above pH 8. In contrast, the use of acidic solutions led to immediate disintegration of these liquid marbles within 10 min, with dispersal of the PDEA-PS latex particles in the aqueous solution. Thus the critical minimum solution pH required for long-term liquid marble stability correlates closely with the known pK(a) value of 7.3 for the PDEA stabilizer chains. Stable liquid marbles were also successfully prepared from aqueous Gellan gum solution and glycerol.

Effect of film thickness and particle size on cracking stresses in drying latex films.

The stress at which latex films crack during drying was investigated using beam bending. Two systems were investigated: (i) poly(methyl methacrylate/butyl acrylate) particles cast as thin films to examine the effect of film thickness on cracking film stress and (ii) polystyrene particles dried as drops to investigate the effect of particle size. Results indicated an inverse relationship between film thickness and film stress, whilst film stress was shown to be independent of the original particle size. These outcomes were in good agreement with Tirumkudulu and Russel's theoretical analysis [M.S. Tirumkudulu and W.B. Russel, Langmuir 21 (2005) 4938], albeit the measured stress values were almost twice the theoretical estimation.

Effect of annealing on the phase structure and the properties of the film formed from P(St-co-BA)/P(MMA-co-BA) composite latex.

Composite latex of P(St-co-BA)/P(MMA-co-BA) was prepared by two-step semi-continuous emulsion polymerization under starved conditions. Optical properties, water resistance and heat aging process of the film formed by the composite latex were examined. It was revealed that annealing temperature played an important role on the structure of the composite latex film. The surface of the film prepared at room temperature was very rough. Many micro-cracks were observed both on the surface and inside of the film. Increase of annealing temperature assisted film formation. There was a critical temperature at which the film properties, such as water resistance and transparency, were significantly improved. However, it was worth to note that phase rearrangement had occurred when the annealing temperature was higher than critical temperature. Micro-pinholes and micro-cracks were detected on the surface of the film. Meanwhile, the properties of the film, such as transparency and water adsorption, became remarkable deteriorated.

Synthesis of biocompatible sterically-stabilized poly(2-(methacryloyloxy)ethyl phosphorylcholine) latexes via dispersion polymerization in alcohol/water mixtures.

Poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) is soluble in either 2-propanol or water but becomes insoluble in certain alcohol-rich 2-propanol/water mixtures. We have exploited this unusual cononsolvency behavior in order to prepare new biocompatible sterically stabilized PMPC latexes via nonaqueous dispersion polymerization in 2-propanol/water mixtures. All polymerizations were conducted in the presence of monomethoxy-capped poly(ethylene glycol) methacrylate (PEGMA) as a reactive stabilizer, with some formulations including ethylene glycol dimethacrylate (EGDMA) as a cross-linker. Under optimized conditions, unimodal size distributions could be obtained with a mean latex diameter of approximately 1 microm, as judged by laser diffraction and DLS. The mean latex diameter depended on both the PEGMA and initiator concentration but was almost independent of the cross-linking density. Smaller PMPC latexes were obtained by increasing the alcohol content of the dispersion medium. On dilution with water, these latexes acquired microgel character. The microgel solution viscosity was insensitive to added salt due to the so-called "antipolyelectrolyte" effect, which is characteristic of polyzwitterions. Finally, copolymerization of MPC with a fluorescein-based methacrylic comonomer produced fluorescently labeled PMPC latexes, which may have potential biomedical applications.

Novel one-pot synthesis of magnetite latex nanoparticles by ultrasound irradiation.

A simple and efficacious procedure for the synthesis of magnetite nanoparticles has been achieved via a sonochemical miniemulsion polymerization process. The sonochemically synthesized magnetite encapsulated polymer latex particles exhibit excellent colloidal stability and strong magnetic properties, and are of a size that makes them technologically relevant. This novel method may be readily extended to the preparation of multiple combinations of different polymers and encapsulated materials.

Latex of immunodiagnosis for detecting the Chagas disease. I. Synthesis of the base carboxylated latex.

This article investigates the synthesis of two (monodisperse, carboxylated, and core-shell) latexes, through a batch and a semibatch emulsion copolymerizations of styrene (St) and methacrylic acid (MAA) onto polystyrene latex seeds. A mathematical model of the process was developed that predicts conversion, average particle size, and surface density of carboxyl groups. The model was adjusted to the batch reaction measurements, and then it was used in the design of the semibatch experiment. The semibatch reaction involved an initial homopolymerization of St followed by instantaneous addition of MAA-St-initiator. Compared with the batch reaction results, the semibatch policy more than doubled the surface density of carboxyl groups. The second part of this series describes the development of an immunodiagnosis latex-protein complex for detecting the Chagas disease, by coupling an antigen of Trypanosoma cruzi onto the produced carboxylated latexes.

Latex of immunodiagnosis for detecting the Chagas disease: II. Chemical coupling of antigen Ag36 onto carboxylated latexes.

A novel immunodiagnosis reagent for detecting the Chagas Disease was developed, by chemical coupling of antigen Ag36 of Trypanosoma cruzi onto two (carboxylated and core-shell) latexes. The coupling reactions involved the use of a carbodiimide intermediate. Bovine serum albumin (BSA) was used as a model protein for determining the appropriate conditions for its physical and chemical coupling. BSA showed an increased adsorption onto the base carboxylated latexes, with respect to a PS latex without carboxyl groups. The chemical bonding experiments only involved the carboxylated latexes. With BSA, the final density of covalently bound protein was 2.30 mg/m(2). In addition, around 55% of the total linked protein was chemically coupled, and the reaction was little affected by the pH. With Ag36, the final density of covalently bound protein was 2.44 mg/m(2), around 80% of the total linked protein was chemically coupled, and the chemical coupling was maximum at pH = 5 (i.e., close to the isoelectric point).

Glycine derived polymerizable cosurfactant in the synthesis of functionalized poly(butyl acrylate) nanolatexes.

The approach of employing N-glycinylmaleamic acid (NGMA) as an efficient cosurfactant to provide microemulsion polymerization of butyl acrylate using a weight ratio of sodium dodecyl sulfate (SDS)/butyl acrylate (BA) at