Block copolymers as polymeric stabilizers in non‐aqueous emulsion polymerization

This review summarizes the background and recent advances of block copolymer stabilized oil‐in‐oil emulsions. For non‐polymerizable emulsions which have promising application possibilities for biomedical and cosmetic formulations, it is shown that tailor‐made block copolymers are by far the most efficient stabilizers with respect to low molecular weight surfactants. The characteristic features of oil‐in‐oil emulsions comprising one polymerizable phase are described. These types of non‐aqueous emulsions are of interest as nanoreactor systems for the polymerization of moisture‐sensitive monomers or catalysts. Furthermore they are the starting point of novel heterophase polymerization processes for the preparation of sterically stabilized polymer particles, as well as of ‘liquid‐filled polymeric materials’. The concept of oil‐in‐oil emulsions is finally extended to those systems where the two phases are polymerizable by distinct polymerization mechanisms. This approach could offer attractive possibilities for the development of special coatings with neither water nor solvent evaporation in their drying or curing step. Copyright © 2011 Society of Chemical Industry     

Pullulan–STMP hydrogels: a way to correlate crosslinking mechanism,structure and physicochemical properties

Rheological and swelling properties of hydrogels based on pullulan crosslinked with sodium trimetaphosphate (STMP) are explained according to various polymer and crosslinking agent concentrations using ³¹P-nuclear magnetic resonance study. This method has allowed determining the amount of all the species present in the medium when varying both pullulan and STMP concentrations. We have clearly demonstrated with a good agreement by both ³¹P-NMR and rheology that a critical STMP concentration occurs which is function of pullulan concentration. This typical crosslinking agent concentration delimitates the maximum of gel structure together with the minimum of swelling.     

Fullerene-functionalized carbon nanotubes as improved optical limiting devices

We report the synthesis, characterization and optical limiting behavior of a nanohybrid built by grafting C₆₀-fullerenes on carbon nanotubes (CNTs). The nonlinear optical limiting properties of the CNT-C₆₀ complex were investigated at wavelengths where C₆₀ does not absorb. We found that the nanohybrid had superior performances to those of CNTs and fullerenes, either taken individually or as a mixture. This enhanced optical limitation of the nanohybrid suggests not only cooperative but also synergistic effects between the two carbon forms. A mechanism involving higher excitonic states of the CNTs formed by Auger recombination of low energy excitons is proposed.     

Vertically oriented nickel nanorod/carbon nanofiber core/shell structures synthesized by plasma-enhanced chemical vapor deposition

Plasma-enhanced chemical vapor deposition, without a nickel-containing gaseous precursor, was used to synthesize continuous nickel (Ni) nanorods inside the hollow cavity of carbon nanofibers (CNFs), thus forming vertically aligned Ni/CNF core/shell structures. Scanning and transmission electron microscopic images indicate that the elongated Ni nanorods originate from the catalyst particles at the tips of the CNFs and that their formation is due to the effect of extrusion induced by the compressive force of the graphene layers during growth. Different from previous work, each vertically-aligned core/shell structure reported is totally isolated from its neighbors. Continuous Ni nanorods are found to separate into smaller ones with increasing growth time, which was ascribed to (i) the limited amount of Ni available in the tip of the CNF, (ii) the polycrystalline nature of the Ni nanorods and (iii) the combined effects of the compressive stresses on the side of the Ni nanorods and of the tensile stress along their axis.     

Random poly(ε‐caprolactone‐L‐alanine) by direct melt copolymerization

A series of random polyesteramides (PEAs) with a range of molar composition from 90/10 to 50/50 were synthesized by direct melt polycondensation of ε‐caprolactone and l ‐alanine. Their structure was fully characterized by Fourier transform IR and NMR spectroscopy. The resulting copolymers are completely amorphous with the exception of PEA‐90/10 which possesses a semicrystalline structure. These PEAs present increasing glass transition temperatures at increasing l ‐alanine contents and exhibit fairly good thermal stability with 10% mass loss temperatures reaching 315 °C. © 2020 Society of Industrial Chemistry     

Divide-and-Conquer Matrisome Protein (DC-MaP) Strategy: An MS-Friendly Approach to Proteomic Matrisome Characterization

Currently, the extracellular matrix (ECM) is considered a pivotal complex meshwork of macromolecules playing a plethora of biomolecular functions in health and disease beyond its commonly known mechanical role. Only by unraveling its composition can we leverage related tissue engineering and pharmacological efforts. Nevertheless, its unbiased proteomic identification still encounters some limitations mainly due to partial ECM enrichment by precipitation, sequential fractionation using unfriendly-mass spectrometry (MS) detergents, and resuspension with harsh reagents that need to be entirely removed prior to analysis. These methods can be technically challenging and labor-intensive, which affects the reproducibility of ECM identification and induces protein loss. Here, we present a simple new method applicable to tissue fragments of 10 mg and more. The technique has been validated on human ovarian tissue and involves a standardized procedure for sample processing with an MS-compatible detergent and combined centrifugation. This two-step protocol eliminates the need for laborious sample clarification and divides our samples into 2 fractions, soluble and insoluble, successively enriched with matrisome-associated (ECM-interacting) and core matrisome (structural ECM) proteins.     

Mechanistic investigation and selectivity of the grafting onto C60 of macroradicals prepared by cobalt-mediated radical polymerization

The grafting mechanism of poly(vinyl acetate) macroradicals prepared by cobalt-mediated radical polymerization onto C₆₀ is investigated. The experimental conditions directly impact the nature and stability of the PVAc/C₆₀ adducts. In the presence of residual initiating radicals that can compete with PVAc° macroradicals for addition onto C₆₀, mixtures of PVAc/C₆₀ adducts having between one and eight polymer chains per C₆₀ are formed. PVAc/C₆₀ adducts prepared with low [PVAc]:[C₆₀] ratios may contain weak C₆₀–C₆₀ bonds that further dissociate and account for the instability of the products. The formation of such dimers can be lessened by increasing the temperature from 30 °C to 100 °C. The temperature increase also allows a complete dissociation of the PVAc-Co dormant species into PVAc° macroradicals and an almost quantitative grafting of eight PVAc chains onto C₆₀, leading to well-defined C₆₀(PVAc)₈ octa-adducts. These results might shed new light on the grafting onto C₆₀ of macroradicals prepared by other CRP techniques.     

Effect of Composition on the Electromechanical Properties of (1-x)Pb(Mg1/3Nb2/3)O3−XPbTiO3 Ceramics

Ceramic lead magnesium niobate–lead titanate ((1-x)PMN_-xPT) of different compositions has been prepared by the columbite precursor method. This study discusses compositions ranging from 0.94PMN–0.06PT to 0.60PM–N0.40PT, focusing on two areas of the (1-x)PMN_xPT system: compositions that exhibit electrostrictive behavior, and those that show piezoelectric behavior. In electrostrictive compositions where x is in the range of 0.06–0.20, the dielectric constant and electromechanical coupling factor dependencies on the bias field are evaluated. The optimal electromechanical properties are obtained with the composition 0.82PMN–0.18PT, measured at temperature T = T_m (the temperature of maximum dielectric constant) = 80°C and with a dc bias of 5 kV/cm. X–ray diffractometry is used to show that the (1-x)PMN_-xPT system has a compositionally wide two–phase region and that 0.655PMN–0.345PT is the morphotropic phase boundary (MPB) composition. Electromechanical property evaluation shows that the optimal piezoelectric properties (piezoelectric charge coefficient ( d₃₃ ) value of 720 pC/N, dielectric constant ( K ) value of 5400, and electromechanical planar and thickness coupling coefficient ( k_p and k_t , respectively) values of 62% and 46%, respectively) are obtained at the MPB composition.     

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one‐component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42759.