Ordered Honeycomb‐Structured Films from Dendronized PMA‐b‐PEO Rod‐Coil Block Copolymers

Summary: Fabrication of honeycomb‐patterned films from amphiphilic dendronized block copolymer (PEO₁₁₃‐b‐PDMA₈₂) by ‘on‐solid surface spreading’ and ‘on‐water spreading’ method is reported. Highly ordered honeycomb films with quasi‐horizontally paralleled double‐layered structure can be fabricated by the on‐solid surface spreading method. This work raises the possibility that such structures can be formed in amphiphilic dendronized block copolymers and extends the family of source materials.

     

Chemical Modification of Chitosan, 17

The Michael reaction of chitosan with acrylic acid was carried out successfully, even in water alone as the reaction medium. As a consequence of its good solubility in water, the reaction product, N‐carboxyethylchitosan, showed excellent biodegradable properties with standard activated sludge.

     

Fabrication and Photocatalytic Activities of Morphology-Controlled Titania Nanoobject Arrays by Block Copolymer Templates

We report a simple scheme to fabricate organic/inorganic hybrid nanostructures with extraordinary morphologies by one-step spin coating, using a PS-b-PEO diblock copolymer as template coupled with sol-gel chemistry. The shape and size of the titania nanoobject can be fine-tuned by controlling the amount of sol-gel precursor relative to PS-b-PEO and the composition of the precursor. Ordered arrays of nanoscopic titania objects such as nanodots, nanobowls, and nanonetworks were obtained from the initial hybrid nanostructures by removing the organic matrix by UV treatment. Photocatalytic activities of the resulting titania nanoobjects were investigated in terms of the degradation of a typical dye.

     

Poly(2‐vinylpyridine)‐block ‐Poly(ϵ‐caprolactone) Single Crystals in Micellar Solution

Self‐assembly of poly(2‐vinylpyridine)‐block‐poly(ϵ‐caprolactone) (P2VP‐b‐PCL) diblock copolymer in the presence of a selective solvent is investigated by transmission electron microscopy and atomic force microscopy. Addition of water into a P2VP‐b‐PCL solution in N,N‐dimethylformamide at 20 °C produces elongated truncated lozenge shaped single crystals of uniform size and shape in large quantities. The single crystals are composed of PCL single‐crystal layer sandwiched between two P2VP layers tethered on the top and bottom basal surfaces. The formation of the single crystals is found to depend on the temperature. These findings provide a facile approach to the preparation of uniform single crystals in large quantities.

     

In situ Localization of Molecules in Crosslinked Particles during Electrohydrodynamic Process: Simple Route to Produce Microcapsules and Fibers with Controlled Release

This study reports a spontaneous selective localization of molecules in crosslinked particles during electrospraying and electrospinning polymer solutions containing the particles. It provides a facile way of preparing microcapsules and fibers with controlled release. The dye molecules were phase separated from the crystalline polymer matrix during the electrohydrodynamic process and moved to the solvent‐rich crosslinked particles. The position of the particles in the microcapsules and fibers could be controlled by adjusting compatibility of the particles with the matrix polymer. The microcapsules and fibers did not show the initial burst release of the molecules and gave considerably prolonged release behavior.

     

Self‐Assembly of Diblock Copolymers into Novel Snowflake‐Shaped Aggregates Driven by Quadruple Hydrogen Bonding

Two well‐defined diblock copolymers with quadruple hydrogen‐bonding groups on one block, denoted PSUEA‐1 and PSUEA‐2 , have been synthesized, and novel snowflake‐shaped nanometer‐scale aggregates, self‐assembled by such diblock copolymers in non‐polar solvents, have been observed. The micellar dimensions were investigated by DLLS and SLLS. Their morphologies were studied by TEM. Since the degrees of polymerization of the Upy‐containing blocks of PSUEA‐1 and PSUEA‐2 are quite similar and the polystyrene block of the PSUEA‐1 is longer than that of the PSUEA‐2 , a subtle but identifiable difference between the sizes and structures of the PSUEA‐1 and PSUEA‐2 aggregates was noticed and characterized.

     

Vapor‐Based Synthesis of Poly[(4‐formyl‐p‐xylylene)‐co‐(p‐xylylene)] and Its Use for Biomimetic Surface Modifications

Summary: The vapor‐based synthesis and characterization of a reactive polymer, poly[(4‐formyl‐p‐xylylene)‐co‐(p‐xylylene)] ( 1 ), have been reported. The reactive polymer coating enables the immobilization of oligosaccharides via the chemoselective aldehyde‐hydrazide coupling reaction.

     

Synthesis of Poly(ethylene oxide)s Bearing Functional Groups along the Chain

Well‐defined poly(ethylene oxide)s (PEOs) bearing reactive sites regularly distributed along the chain have been synthesized by the polycondensation of PEO containing a central tertiary amino group with dichloromethane, followed by quaternization with suitable reagents to obtain polyzwitterionic or cationic PEOs with alkyl, allyl, or fluorocarbon pendant groups. The pendant allyl groups have been converted into primary amino groups by reaction with 2‐aminoethanethiol hydrochloride to obtain polyamino‐functionalized PEO.

Polyfunctional PEOs bearing different pendant groups.     

Novel Top‐Surface Imaging Process by Selective Chemisorption of Poly(dimethyl siloxane) on Diazoketo‐Functionalized Single Component Photoresist

A novel top‐surface imaging process was successfully established using selective chemisorption of amine‐functionalized poly(dimethyl siloxane) onto the carboxylic groups formed on the surface of diazoketo‐functionalized polymer film by UV light irradiation. The chemisorbed poly(dimethyl siloxane) worked as an efficient etch mask for the subsequent oxygen plasma etching process for pattern generation. High‐resolution patterns were resolved with the new imaging process.

     

Initiated Chemical Vapor Deposition of Poly(furfuryl methacrylate)

Furan ring‐functionalized solid surfaces are achieved by the initiated chemical vapor deposition (iCVD) method, a solvent‐free process to form films under mild conditions. The polymerization of furfuryl methacrylate monomer is initiated by a resistively heated filament wire. The functionality of the furan group in the iCVD film enabled Diels–Alder chemistry with 4‐phenyl‐1,2,3‐triazolin‐3,5‐dione (N‐PTD).

     

Modeling of the Phase Separation Behavior of Polydisperse Semi‐Flexible Diblock Copolymers

Summary: A modified random phase approximation method with a cumulant expansion for the semi‐flexible structure factor of diblock copolymers was exercised to describe the phase separation behavior of semi‐flexible and polydisperse diblock copolymers. Scattering curves and spinodal diagrams were calculated applying monomer specific input parameters. The influence of polydispersity was included applying basic concepts of mathematical statistics utilizing several probability density distributions in the case of the two single blocks. In contrast to semi‐flexibility, the main effect of polydispersity was found to shift the spinodal up, thus to enlarge the range of existence of the homogeneous phase.

Twofold Schultz‐Zimm distribution of diblock copolymers.     

Observations on Solution Crystallization of Poly(vinyl alcohol) in the Presence of Single‐Wall Carbon Nanotubes

PVA/SWNT dispersions yield aloe plant‐like crystals, where the leaves are single crystals templated by PVA coated SWNT. Longer growth times (≈18 months) lead to hexagonal rod‐like crystals. HR‐TEM images show evidence that PVA molecules are aligned parallel to the SWNT axis. WAXD, electron diffraction, and HR‐TEM observations of these aloe plant and hexagonal crystals suggests evidence for possible PVA‐SWNT epitaxy. Wide‐angle and electron diffraction data of these crystals also show that the structure seems to mimic the 2D hexagonal crystal packing of SWNT. PVA lattice images and moiré fringes were also observed in the leaf‐like crystals.

     

Preparation of Magnetite Nanoparticles Coated with an Amphiphilic Block Copolymer: A Potential Drug Carrier with a Core‐Shell‐Corona Structure for Hydrophobic Drug Delivery

Summary: The synthesis of magnetic magnetite nanoparticles coated with amphiphilic block copolymers of poly(ethyl methacrylate)‐block‐poly(2‐hydroxyethyl methacrylate) for use as new potential carriers for hydrophobic drug delivery is reported. The results show that a new core‐shell‐corona structural material is obtained with a very narrow molecular weight distribution of the hydrophobic segment (PDI = 1.10). UV‐Vis results show that 37% of progesterone is released from the nanoparticles after 22 h, much slower than free release (99% after 14 h), which demonstrates that the presence of the hydrophobic segment can effectively control the release of hydrophobic drugs.

Synthesis of an amphiphilic block polymer poly(ethyl methacrylate)‐block‐poly(2‐hydroxyethyl methacrylate) on magnetite nanoparticles and their use as potential drug carriers     

Ring and Disk‐Like CdSe Nanoparticles Stabilized with Copolymers

CdSe nanoparticles stabilized with the amphiphilic diblock copolymer polystyrene‐block‐poly(4‐vinylpyridine) were spread from toluene dispersion on the water surface. Monolayers could be transferred onto solid substrates using the Langmuir‐Blodgett technique. By means of atomic force and scanning electron microscopy highly symmetric ring and disk‐like structures with diameters ranging between 150 nm and 1200 nm were observed.

AFM image of a mixed monolayer of copolymer 12 and CdSe nanoparticles stabilized with polystyrene‐block‐poly(4‐vinylpyridine).     

Low‐Density Polyethylene (LDPE) Surface With a Wettability Gradient by Tuning its Microstructures

Summary: We describe an interesting approach to the fabrication of wettability gradients from hydrophobicity to superhydrophobicity in low‐density polyethylene (LDPE) films by first forming high porosity surfaces and placing the specimens onto linear temperature gradients. While the polymer chosen for the study is non‐polar, its microporous layer provides sufficient superhydrophobicity. Lateral gradient heating of the layer results in partial melting of the polymer and correspondingly decreases porosity thus decreasing hydrophobicity.

     

Green Nanocomposites from Renewable Resources: Biodegradable Plant Oil‐Silica Hybrid Coatings

Green nanocomposite coatings based on renewable plant oils have been developed. An acid‐catalyzed curing of epoxidized plant oils with 3‐glycidoxypropyltrimethoxysilane produced transparent nanocomposites. The hardness and mechanical strength improved by incorporating the silica network into the organic polymer matrix, and good flexibility was observed in the nanocomposite. The nanocomposites showed high biodegradability.

     

Preparation of Binary Conductive Polymer Composites with Very Low Percolation Threshold by Latex Blending

The communication reports a way to prepare carbon black (CB)/waterborne polyurethane conducting composites with percolation thresholds as low as 0.2 vol.‐% through conventional latex blending. CB particles in the composites appear segregated in their distribution and are located in the two‐dimensional interstices among the polymer domains. The intimate filler/matrix interaction also improves the tensile strength of the matrix at the CB content corresponding to the electrical percolation threshold.

Room temperature conductivity, σ, and tensile strength as a function of carbon black (CB) concentration of the waterborne‐polyurethane‐based composites prepared by latex blending.     

Selective Guest Uptake from Solvent Mixtures in the Clathrate Phase of Syndiotactic Polystyrene

Summary: Selective absorption uptake during the guest‐exchange processes in the δ form of syndiotactic polystyrene (sPS) was confirmed by IR spectroscopy. When films of the δ form were immersed in hexane/decane or chloroform/decane mixtures, decane molecules were incorporated preferentially in the δ form. Sorbate uptake by the δ form was greatly accelerated when the sorbate was mixed with a solvent penetrable to the amorphous region of sPS.

Concentration changes in a δ‐form film during sorption processes: sorption of a chloroform(D)/decane(H) mixture (1:1 molar ratio).