Emulsion polymerization: radical segregation and its role in controlled polymerization

A numerical approach based on a recently proposed discretization technique and suitable for molecular weight calculation in emulsion polymerization is presented. The main features of this approach are (i) the direct evaluation of the complete chain length distribution without the need of predefined model distributions (as in the case of moment based methods), (ii) the large flexibility when defining the computational grid, (iii) the capability of evaluating with accuracy two integral properties of the distribution no matter how coarse the grid is and (iv) the limited computational effort required. Selected applicative examples are reported with emphasis on cases where other computational approaches give unreliable or less detailed results.     

Fixed point for set-valued mappings satisfying an implicit relation in partially ordered metric spaces

Let (X,?) be a partially ordered set and d be a complete metric on X. Let F,G be two set-valued mappings on X. We obtained sufficient conditions for the existence of common fixed point of F and G satisfying an implicit relation in partially ordered set X.     

Microwave-assisted synthesis of functional electrode materials for energy applications

Functional electrode materials play an increasingly important role in the advancement of energy conversion and storage technologies used in batteries, electrolyzers, supercapacitors, fuel cells, and other electrochemical devices. To address the problems related to accelerating demand for the so-called renewable energy, which are simultaneously coupled with environmental concerns, new generations of materials, engineering methodologies, and innovative techniques are necessary. Among many synthetic methods, microwave-assisted synthesis becomes nowadays a very popular approach to efficiently control both the composition and morphology of solids. In this review, we focus on its applications to create new advanced energy electrode materials.

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Graphical abstract A schematic illustration of microwave-assisted synthesis process for making functional electrode materials

     

Hierarchical Self‐Assembly of PDMA‐b‐PS Chains into Granular Nanoparticles: Genesis and Fate

The hierarchical self‐assembly of an amphiphilic block copolymer, poly(N,N‐dimethylacrylamide)‐block‐polystyrene with a very short hydrophilic block (PDMA₁₀‐b‐PS₆₂), in large granular nanoparticles is reported. While these nanoparticles are stable in water, their disaggregation can be induced either mechanically (i.e., by applying a force via the tip of the cantilever of an atomic force microscope (AFM)) or by partial hydrolysis of the acrylamide groups. AFM force spectroscopy images show the rupture of the particle as a combination of collapse and flow, while scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of partly hydrolyzed nanoparticles provide a clear picture of the granular structure.

     

Self-induced transparency in diblock copolymer dispersions

We report on the versatile effect of weak red laser light impinging on diblock copolymer [poly(isoprene-b-styrene)] dispersions in two selective solvents for each block. In the strongly scattering but transparent micellar solutions in hexane (a good solvent for polyisoprene), higher refractive index copolymer-rich fibers were formed. In the turbid dispersions of the same copolymer in ethyl acetate (a good solvent for polystyrene), the effect of self-induced transparency was observed. A two-step patterning mechanism caused the generation of a transparent microchannel, increasing light transmission. The analogy between the current effect and that observed in homopolymer polyisoprene solutions in different solvents is discussed toward an understanding of the unanticipated light-soft-matter interaction.     

Electrooxidation of chloro, nitro, and amino substituted phenols in aqueous medium and their heterogeneous kinetics

The present study deals with the electrochemical investigation of seven different phenols through cyclic voltammetry (CV). Phenols can be partly eliminated from aqueous solutions by electrochemically initiated polymerization. Thus, the basic CV behavior was studied under the optimized conditions such as; pH of the medium, concentration of the analyte, the supporting electrolyte, potential window, and scan rate. The CV curves of all of the phenols showed that the electro-polymerization phenomenon on the electrode surface causes surface fouling for further electrooxidation of these compounds. The influence of substituents in the ring was especially noted in terms of their tendency to foul the electrode surface. The formation of new intermediates during the electrooxidation was observed whose nature was found to be highly dependent on the type and position of the substituent. As far as the influence of pH is concerned, phenols in basic medium were electrooxidized earlier but with low current. Difference in CV response because of the substituent attached under varied pH was also noted. From the diffusion coefficient (D) and heterogeneous rate constant (k _sh) mixed nature of electron transfer process was proposed.     

Monitoring the Dynamics of Phase Separation in a Polymer Blend by Confocal Imaging and Fluorescence Correlation Spectroscopy

The phase separation of the polymer blend polystyrene/poly(methyl phenyl siloxane) (PS/PMPS) is studied in situ by laser scanning confocal microscopy (LSCM) and by fluorescence correlation spectroscopy (FCS) at macroscopic and microscopic length scales, respectively. It is shown for the first time that FCS when combined with LSCM can provide independent information on the local concentration within the phase‐separated domains as well as the interfacial width.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Photo- and Electrochemical Dual-Responsive Iridium Probe for Saccharide Detection

Dual detection systems are of interest for rapid, accurate data collection in sensing systems and in vitro testing. We introduce an Ir^III complex with a boronic acid receptor site attached to the 2-phenylpyridine ligand as an ideal probe with photo- and electrochemical signals that is sensitive to monosaccharide binding in aqueous solution. The complex displays orange luminescence at 618 nm, which is reduced by 70 and 40 % upon binding of fructose and glucose, respectively. The electro-chemiluminescent signal of the complex also shows a direct response to monosaccharide binding. The Ir^III complex shows the same response upon incorporation into hydrogel matrices as in solution, thus demonstrating the potential of its integration into a device, as a nontoxic, simple-to-use tool to observe sugar binding over physiologically relevant pH ranges and saccharide concentrations. Moreover, the complex's luminescence is responsive to monosaccharide presence in cancer cells.     

Dermal Tattoo Biosensors for Colorimetric Metabolite Detection

Tattooing is a ubiquitous body modification involving the injection of ink and/or dye pigments into the dermis. Biosensors in the form of tattoos can be used to monitor metabolites in interstitial fluid. Here, minimally invasive, injectable dermal biosensors were developed for measuring pH, glucose, and albumin concentrations. The dermal pH sensor was based on methyl red, bromothymol blue, and phenolphthalein, which responded to a pH range from 5.0 to 9.0. The dermal glucose sensor consisted of glucose oxidase, 3,3′,5,5′‐tetramethylbenzidine, and peroxidase that detected concentrations up to 50.0 mmol L^?1. The dermal albumin sensor consisted of 3′,3′′,5′,5′′‐tetrachlorophenol‐3,4,5,6‐tetrabromosulfophthalein to measure concentrations up to 5.0 g L^?1. The sensors were multiplexed in ex vivo skin tissue and quantitative readouts were obtained using a smartphone camera. These sensors can be used to manage of acid–base homeostasis, diabetes, and liver failure in point‐of‐care settings.