A Superhydrophobic Surface Fabricated by an Electrostatic Process

We describe the fabrication of a biomimically designed superhydrophobic poly(ε‐caprolactone) surface, which was obtained using a modified electrostatic process. The fabricated surface exhibits a micron‐sized pyramid structure consisting of accumulated droplets and nanofibres. By using this simple one‐step process, we can achieve a superhydrophobic surface having both a high water contact angle and low threshold sliding angle, similar to that of the superhydrophobic plant leaf.

     

Poly(ethylene glycol) Surface Coated Magnetic Particles

Summary: A methacrylate‐functionalized poly(ethylene glycol) macromonomer was copolymerized at the surface of methacrylate‐derivatized maghemite nanoparticles. After silylation of the magnetic core with methacryloxypropyltrimethoxysilane, two grafting procedures based on either a direct copolymerization reaction in water or an inverse emulsion polymerization were compared. A direct copolymerization led to low polymer surface amounts, whereas an inverse emulsion process allowed nanocomposite particles containing up to 90 wt.‐% polymer to be obtained.

TEM picture of maghemite‐PEG hybrid particles.     

Nickel(II) α‐Diimine Catalyst for Grignard Metathesis (GRIM) Polymerization

A nickel α‐diimine catalyst was used for Grignard metathesis (GRIM) polymerization of 2,5‐dibromo 3‐hexylthiophene and 2‐bromo‐5‐iodo‐3‐hexylthiophene monomers. GRIM polymerization of 2‐bromo‐5‐iodo‐3‐hexylthiophene generated regioregular polymers with molecular weights ranging from 3 000 to 12 000 g · mol⁻¹. The nickel α‐diimine catalyst was also successfully used for the GRIM polymerization of a bulky benzodithiophene monomer.

     

Anisotropic Electronic Conductivity in Layer‐By‐Layer Composite Film Composed of Water‐Soluble Conjugated Polymers and SWNTs

This paper reports the anisotropic electrical properties of a layer‐by‐layer (LBL) film composed of water‐soluble conjugated polymers and single‐walled carbon nanotubes (SWNTs). The water‐soluble poly (p‐phenylene ethynylene)s (PPEs) are capable of a strong π‐π interaction with the sidewall of SWNTs and results in a very stable PPE‐SO₃/SWNTs composite in aqueous solution. Aligned LBL films were prepared by self‐assembly using the anionic PPE/SWNTs and cationic PPE on various substrates. The polarized Raman spectra exhibited the cos²α polarization dependence of the G‐band intensity between the polarization direction and the SWNTs alignment direction. The electric conductivity within the LBL films can be controlled by the deposition direction in the LBL formation.

     

Multicomb Polymeric Supramolecules and Their Self‐Organization: Combination of Coordination and Ionic Interactions

Several alkyl side chains are bonded to each polymeric repeat unit using both coordinated ligands and electrostatically bound counterions to directly control the interface curvature of the self‐organized structures. 2,6‐Bis(octylaminomethyl)pyridine is Zn‐coordinated to poly(4‐vinylpyridine) (P4VP) with dodecylbenzenesulfonate (DBS) counterions, leading to multicomb polymeric supramolecules, poly[(4VP)Zn(2,6‐bis(octylaminomethyl)pyridine)(DBS)₂]. Coordination is evidenced by infrared spectroscopy and visualized by quantum chemical calculations. The amorphous hexagonal self‐organized structures are characterized using X‐ray measurements.

     

Sonochemical Synthesis of Magnetic Protein Container for Targeted Delivery

A new targeted delivery system was developed in this paper by depositing magnetic NPs on protein containers which were prepared by sonicating oil in a protein solution. The deposition was conducted by layer‐by‐layer technique and monitored by zeta potential measurement. Such prepared samples can be targeted delivery in an external magnetic field. The hydrophobic dye TPP, as a model of drug, was loaded in the containers by dissolution in the oil phase before sonication. The containers loaded with dye are stable and can sustain the deposition treatment without loss of dye due to the protection of protein nanoshells.

     

Synthesis and Self‐Assembly of Styrene–[1]Dimethylsilaferrocenophane–Methyl Methacrylate Pentablock Copolymers

Summary: Well‐defined pentablock copolymers of styrene–[1]dimethylsilaferrocenophane–methyl methacrylate (PMMA‐b‐PFS‐b‐PS‐b‐PFS‐b‐PMMA) are synthesized using lithium naphthalide as initiator and a 1,1‐dimethylsilacyclobutane‐mediated 1,1‐diphenylethylene (DPE) end‐capping technique. Annealing under various conditions followed by analysis by transmission electron microscopy revealed good phase separation by the copolymers and the presence of ordered microstructures, such as spheres‐on/in‐spheres, and spheres‐on/in‐lamellae micromorphologies.

Structure of the styrene–[1]dimethylsilaferrocenophane–methyl methacrylate pentablock copolymers.     

Regioregularity in Poly(3‐alkoxythiophene)s: Effects on the Faraday Rotation and Polymerization Mechanism

Summary: Poly(3‐alkoxythiophene)s with different degrees of regioregularity were prepared using three different methodologies. It is shown that their Faraday rotation is highly dependent on the degree of regioregularity. The origin of the differences in regiospecificity of the methodologies is discussed.

Structure of the polymer pol 3 .     

Hydrogen Bonding‐Induced Transformation of Network Aggregates into Vesicles ‐ A Potential Method for the Preparation of Composite Vesicles

While network‐like assemblies are formed by amphiphilic polyphosphazenes with poly(N‐isopropylacrylamide) and ethyl tryptophan as side groups in aqueous solution, a significant morphology transformation is observed when small molecules that exhibit hydrogen‐bonding interactions with amphiphilic copolymers are introduced during the preparation of polymeric assemblies through a dialysis procedure. Depending on copolymer composition and the content of small molecules introduced, aggregates ranging from general vesicles, high‐genus vesicles, to well‐defined nanospheres can be prepared successfully as clearly evidenced by TEM observation, which suggests this procedure should be a novel approach to prepare composite vesicles.

     

Polyelectrolyte Multilayer Microspheres as Carriers for Bienzyme System: Preparation and Characterization

Summary: Polyelectrolyte multilayer microspheres were prepared by alternating adsorption of dextran sulfate and protamine on melamine formaldehyde cores followed by the partial decomposition of the core. Peroxidase and glucose oxidase were immobilized in the prepared microspheres. Retention of enzymatic activity of the peroxidase/glucose oxidase system incorporated into the microspheres was demonstrated. Applicability of the bienzyme system immobilized in the microspheres for kinetic glucose assay was shown.

SEM image of the polyelectrolyte multilayer microsphere.     

Synthesis of Conjugated Polymer Nanoparticles in Non‐Aqueous Emulsions

Summary: A novel non‐aqueous emulsion system, consisting of cyclohexane as the continuous and acetonitrile as the dispersed phase, is described. Stabilization of the system can be achieved by using polyisoprene‐block‐poly(methyl methacrylate) copolymers as emulsifiers. The suitability of this system for performing water‐sensitive, catalytic, and oxidative polymerizations and polycondensations is demonstrated by the synthesis of poly(3,4‐ethylenedioxythiophene), poly(thiophene‐3‐yl‐acetic acid), and polyacetylene. In all cases spherical nanoparticles with diameters as small as 23 nm can be obtained.

     

Highly Ordered Hexagonal Arrays of Hybridized Micelles from Bimodal Self‐Assemblies of Diblock Copolymer Micelles

We demonstrate the formation of highly ordered hexagonal arrays of hybridized polystyrene–poly(4‐vinyl pyridine), PS–PVP, micelles with controllable size by solvent annealing techniques. Because the formation of hybridized micelles was prohibited in the mixture solutions of two different‐sized PS–PVP micelles, single‐layered films with bimodal self‐assemblies of small and large micelles were fabricated from the mixture solutions by adjusting their mixing ratios. When the single‐layered films were solvent annealed by saturated vapor of tetrahydrofuran (THF), on the other hand, small and large PS–PVP micelles in the bimodal self‐assemblies merged together to form hybridized micelles. In addition, the hybridized micelles arranged themselves in a highly ordered hexagonal array, the diameter and center‐to‐center distance of which were precisely adjusted by varying the mixing ratio of small to large micelles in the bimodal assemblies.

     

Synthesis of Block Copolymers Modified with Phosphonate Ester Groups Using Nitroxide‐Mediated Radical Polymerization

Summary: Phosphonate groups were introduced into block copolymers of styrene derivatives either as single end‐groups or as small blocks using nitroxide‐mediated radical polymerization. In order to combine the hydrophobic and hydrophilic segments, block copolymers with N,N‐dimethyl acrylamide were synthesized. After hydrolysis to phosphonic acid groups, adsorption of the polymer onto metal oxides was possible.

Conversion of the phosphonate groups by transesterification with trimethylbromosilane (TMBS), followed by hydrolysis of the silylester group.     

A Physical Method of Fabricating Hollow Polymer Spheres Directly from Oil/Water Emulsions of Solutions of Polymers

Summary: A new physical method of fabricating hollow spheres from different polymers has been developed. In this method, emulsions were prepared by mixing organic solutions of polystyrene, poly(D ,L ‐lactide‐co‐glycolide) (PLGA), and bacterial poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), water, and surfactants. The evaporation of solvents at room temperature caused a phase separation that eventually yielded hollow spheres. Molecular weights, concentrations of polymers, and the natures of surfactant and solvent were important aspects of hollow sphere formation and structure. A mechanism for the formation of hollow spheres is proposed based on observations made using an optical microscope equipped with a digital camcorder and using scanning electron microscopy images of hollow spheres obtained under different conditions.

A scanning electron microscopy image of a broken smaller hollow sphere prepared using a 7 wt.‐% polystyrene solution (diameter of the sphere ∼10 micrometers).     

A New Simulation Algorithm with Revised “Association Criteria” for Studying the Association of Heteroarm Star Copolymers

Summary: A new computational algorithm for dynamic lattice Monte Carlo simulations of the associative behavior of heteroarm copolymers in selective solvents was developed and optimized for efficient and relatively fast simulation studies. The algorithm is based on the Siepmann and Frenkel variant of the bias self‐avoiding walk procedure. Simultaneously, a new criterion for recognition of an associate was proposed. The first results on the micellization of heteroarm star copolymers are presented.

     

Surfactant‐Free Spinning of Composite Carbon Nanotube Fibers

Summary: Fibers and yarns are promising forms to use and control the spatial orientation of carbon nanotubes in macroscopic materials. Various approaches have been proposed in the last few years to achieve fibers with a fraction of carbon nanotubes. Among them, coagulation spinning in aqueous media has proven to be a simple and capable method of leading to super‐tough materials. However, all water‐based processes described so far have made use of surfactant‐stabilized carbon nanotubes. In the present work, a method is shown to spin fibers from surfactant‐free nanotube solutions while preserving an all water‐based process. The resultant fibers exhibit mechanical and electrical properties that compare well with those of previously reported fibers spun with surfactants. The fibers exhibit a significant toughness and a high electrical conductivity.

Scanning electron micrograph of the fiber, showing the surface texture.     

Synthesis of Polyaniline‐Vanadium Oxide Nanocomposite Nanosheets

Summary: Polyaniline‐vanadium oxide nanocomposite nanosheets with thickness between 10 and 20 nm, and lateral dimensions in the range of hundreds of nanometers to several microns have been synthesized by in situ intercalation polymerization of aniline with layered V₂O₅ under hydrothermal conditions. The product was characterized by field‐emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT‐IR) spectroscopy, and X‐ray diffractometer (XRD). The effects of the concentration of aniline and reaction temperature on the morphologies of polyaniline‐vanadium oxide nanocomposites have also been investigated.

SEM image of tremella‐like polyaniline‐vanadium oxide nanocomposite nanosheets.