Synthesis of a Multi Alternating‐Arm‐Containing Dendritic Star Copolymer by RAFT and Cationic Ring‐Opening Polymerization

A new dendritic heteroarm star copolymer that contains multi‐alternating arms of poly(ethylene oxide‐tetrahydrofuran) (P(EO‐THF)) and poly(methyl methacrylate) (PMMA) on a dendritic polyester core has been synthesized by a ‘core‐first’ approach by combination of sequential cationic ring‐opening polymerization (CROP) and reversible addition–fragmentation transfer (RAFT) polymerization initiated by a dendritic macroinitiator ( 3 ) capped with multi‐alternating terminal carboxylic acid groups (used directly to initiate the ROP of THF in the presence of EO as a polymerization promoter to attain P(EO‐THF) arms) and dithiobenzoate groups (used to initiate RAFT polymerization of MMA to attain PMMA arms). The structures of the products were confirmed by NMR spectroscopy, GPC‐MALLS, and DSC measurements.

     

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).

     

Direct Synthesis of PVA‐g‐PDMS in Microsuspension

The synthesis of P(VA‐co‐VAc)‐graft‐PDMS copolymers has been achieved in microsuspension by direct reaction between an epoxy‐terminated PDMS and some pendant alcohol groups in P(VA‐co‐VAc). In this synthesis, the copolymer is used both as dispersant and reactant. The hydrophilic/hydrophobic character of the final material can be varied at will by incorporating various contents of epoxy‐functionalized PDMS through optimized reaction conditions. The final composition was determined by TGA and ¹H NMR. Products prepared from monofunctional PDMS were easily redispersed in water whereas a film of crosslinked materials, arising from difunctional PDMS, showed the best waterproofing as shown by contact angle analysis.

     

Novel Wormlike Nanostructures Self‐Assembled in a Well Defined Liquid Crystalline Diblock Copolymer with Azobenzene Moieties

Novel wormlike nanostructures were self‐assembled in bulk films of a well defined diblock copolymer with azobenzene moieties, which was prepared by atom transfer radical polymerization (ATRP). For comparison, a homopolymer with almost the same repeat units of azobenzene as those in the copolymer was also prepared. They both had well defined structures and exhibited a smectic liquid crystalline phase. Upon annealing the copolymer films, poly(methyl methacrylate) formed a matrix with excellent optical properties, and the azobenzene segment in the minority phase self‐assembled into a wormlike mesogenic domain in the bulk films. Such block copolymer films exhibited stability and transparency by eliminating the scattering of visible light, indicating their potential application as photoresponsive functional materials. Although wormlike morphologies have been obtained in micelles from block copolymer solutions, to the best of our knowledge, such wormlike nanostructures have never been explored in bulk films.

     

Polyaniline “Nanotube” Self‐Assembly: The Stage of Granular Agglomeration on Nanorod Templates

The identification and control of a critical stage of polyaniline “nanotube” self‐assembly is presented, namely the granular agglomeration or growth onto nanorod templates. When the synthesis pH is held above 2.5, smooth insulating nanorods exhibiting hydrogen bonding and containing phenazine structures are produced, while below pH 2.5, small 15–30 nm granular polyaniline nanoparticles appear to agglomerate onto the available nanorod surface, apparently improving conductivity of the resulting structures by three orders of magnitude. This finding affects both fundamental theories of polyaniline nanostructure self‐assembly and their practical applications.

     

Towards Multipotent Coatings: Chemical Vapor Deposition and Biofunctionalization of Carbonyl‐Substituted Copolymers

Future advances in designing bioactive materials, such as antithrombotic coatings for cardiovascular stents, will require widely applicable and robust methods of surface modification. In this paper, we report on the development of multifunctional polymer coatings made by chemical vapor deposition (CVD) copolymerization. Polymer coatings of various [2.2]paracyclophane derivatives were co‐deposited in controlled ratios and their chemical composition verified by FT‐IR and X‐ray photoelectron spectroscopy. Furthermore, preliminary biocompatibility of these coatings was assessed using human umbilical vein endothelial cells and 3T3 murine fibroblasts. The parallel immobilization of two different antithrombotic biomolecules onto a CVD‐based copolymer is also demonstrated by orthogonal immobilization strategies.

     

Plasma‐Initiated Controlled/Living Radical Polymerization of Methyl Methacrylate in the Presence of 2‐Cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN)

Summary: Plasma‐initiated controlled/living radical polymerization of methyl methacrylate (MMA) was carried out in the presence of 2‐cyanoprop‐2‐yl 1‐dithionaphthalate. Well‐defined poly(methyl methacrylate) (PMMA), with a narrow polydispersity, could be synthesized. The polymerization is proposed to occur via a RAFT mechanism. Chain‐extension reactions were also successfully carried out to obtain higher molecular weight PMMA and PMMA‐block‐PSt copolymer.

Dependence of ln([M]₀/[M]) on post‐polymerization time (above), and \overline M _{\rm n} and PDI against conversion (below) for plasma initiated RAFT polymerization of MMA at 25 °C.     

Effect of Turbulent Flow on Coil‐Globule Transition of λ‐DNA

Summary: The addition of spermidine (SPD) into turbulent flow as a condensing agent showed the abrupt change of turbulent drag reducing (DR) efficiency of λ‐DNA in turbulent flow for the first time. The resultant asymptote DR efficiency explains the origin of those changes, which can be conclusively verified via the electrophoresis experiment. Despite the different fluid conditions, with and without condensing agent, all λ‐DNA molecules possessed the same half‐cut dimension, implying that the discrete change of DNA conformation can dramatically alter the flow characteristics.

Coil‐globule transition of DNA by spermidine.     

Preparation of Antimicrobial Ultrafine Cellulose Acetate Fibers with Silver Nanoparticles

Summary: A feasible method for the preparation of antimicrobial ultrafine fibers with silver nanoparticles was developed by direct electrospinning of a cellulose acetate (CA) solution with small amounts of silver nitrate followed by photoreduction. Silver nanoparticles in ultrafine CA fibers were stabilized by interactions with carbonyl oxygen atoms in CA. Ultrafine CA fibers with silver nanoparticles showed very strong antimicrobial activity.

TEM image of an ultrafine CA fiber electrospun from 10 wt.‐% CA solution with 0.5 wt.‐% AgNO₃.     

Synthesis of π‐Conjugated Polymer Consisting of Pyrrole and Fluorene Units by Ru‐Catalyzed Site‐Selective Direct Arylation Polycondensation

Polycondensation of 1‐(2‐pyrimidinyl)pyrrole with 2,7‐dibromo‐9,9‐dioctylfluorene via Ru‐catalyzed direct arylation gives the corresponding conjugated polymer with a molecular weight of 19 800 in 86% yield. The introduction of directing group, 2‐pyrimidinyl substituent, into the pyrrole monomer induces ortho‐metalation and provides the site‐selective direct arylation polycondensation at the α‐position of pyrrole unit without the protection of β‐position. The removal of 2‐pyrimidinyl substituent on the pyrrole unit proceeds efficiently and results in the enhancement of coplanarity along the main chain of the polymer.

     

Direct Ion Exchange Self‐Metallization: A Novel and Efficient Route for the Preparation of Double‐Surface‐Silvered Polyimide Films

Summary: Silvered polyimide films have been fabricated by direct ion exchange of a damp‐dry poly(amic acid) film with an aqueous silver solution such as silver nitrate. Thermal curing of the silver(I )‐containing films under tension leads to cycloimidization of the poly(amic acid) into polyimide with a concomitant silver(I ) reduction and aggregation at both film sides to give reflective and conductive double‐surface‐silvered polyimide films. The metallized films retain the essential properties of the parent polyimide.

Surface morphology of the prepared double‐surface‐silvered polyimide films.     

Self‐Assembling Nanomaterials using Magnetic Nanoparticles Modified with Polystyrene Brushes

Magnetic nanomaterials have been studied in order to generate novel nanocomposites that display both the magnetic properties of the nanoparticles and the ability to self‐assemble of the amorphous block copolymer matrix. Towards this goal, iron oxide magnetic nanoparticles have been modified with PS brushes by ATRP in order to improve both the dispersion and the affinity of the nanoparticles with one of the blocks of a polystyrene‐block‐polybutadiene‐block‐polystyrene block copolymer. This method of preparation of nanocomposites opens new strategies for the generation of magnetic nanomaterials. The samples are characterized using DSC and atomic and magnetic force microscopies.

     

Ethylene and Ethylene/Propylene Polymerization Behavior of Bis(phenoxy‐imine) Zr and Hf Complexes with Perfluorophenyl Substituents

The catalytic properties of bis(phenoxy‐imine) Zr and Hf complexes incorporating perfluorophenyl groups with methylaluminoxane were investigated. The fluorinated complexes produced far higher‐molecular‐weight polyethylenes and ethylene/propylene copolymers with increased activities compared with the non‐fluorinated congeners. Moreover, the fluorinated complexes displayed a higher incorporation ability for propylene.

Structures of complexes 1 – 4 .     

Addition‐Fragmentation Chain Transfer Involving Dimers of α‐Methylvinyl Monomers Studied by ESR Spectroscopy: Competition between Fragmentation and Bimolecular Termination

Detection of the adduct radical by ESR spectroscopy and after‐effect ESR measurements of the adduct radical concentrations in the photosensitized polymerization of styrene (St) in the presence of dimers of α‐methylstyrene (MSD) and methyl methacrylate have revealed that the dominant mechanism of adduct radical loss changes from bimolecular termination to fragmentation as the temperature is increased beyond 90 °C for St/MSD.

     

Easy One‐Pot Synthesis of a Reactive Hydrogel from Commercially Available 2‐Isocyanatoethyl Methacrylate and K2S2O5

Addition of commercially available 2‐isocyanatoethyl methacrylate to a water solution of potassium bisulfite unexpectedly yields an anionically charged hydrogel. Structural analysis shows the presence of sulfonato‐blocked isocyanates (with no detectable residual isocyanates), a full polymerization of the vinyl groups, and the appearance of urea functional groups. A mechanism is proposed to explain the gel formation, based on a combination of bisulfite‐initiated free‐radical polymerization, crosslinking by urea bridge formation, and addition of bisulfite ions to isocyanate groups. Some basic physical properties (TGA, swelling) of the gel are presented.

     

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.

     

Binary Reactive/Inert Non‐Fouling Polymeric Surfaces

Binary reactive/inert antifouling polymer brushes were grafted via a two step surface initiated polymerization from printed initiator monolayer and provided robust, effective polymeric surfaces for bioattachment with distinguishably reduced non‐specific adsorption. This synthetic strategy can be harnessed to build complex binary polymeric structures on substrate surfaces and the polymer brush surfaces reported in the present paper can be widely used for versatile biological study.

     

Synthesis,Characterization, and Mechanism of Polymerization of Poly(but‐2‐ene sulfide)

Summary: The effect of structural factors on polymer formation versus cyclization is reported. The reaction of sodium sulfide with either 1,4‐dibromobut‐2‐ene 1 or 1,4‐dibromobutane 2 has been carried out in presence of a phase transfer catalyst and it was observed that the former yields polymer, whereas the latter gives cyclic and linear products. Interestingly, trans/cis isomerization takes place during the polymer formation from 1 and a plausible mechanism has also been discussed.

The reaction mechanism for unsaturated compound 1 and saturated compound 2 is discussed here.     

Macromolecular Recognition by Polymer‐Carrying Cyclodextrins: Interaction of a Polymer Bearing Cyclodextrin Moieties with Poly(acrylamide)s Bearing Aromatic Side Chains

Summary: The interaction of a polymer bearing β‐cyclodextrin moieties (β‐CD polymer) with poly(acrylamide)s bearing aromatic side chains was investigated by viscometry to study the effect of collectivity (i.e., interactions at multi‐sites) in macromolecular recognition. The formation of inclusion complexes at multi‐sites caused a large difference in the size of interpolymer aggregates, even though the difference in association constants for complexation of native β‐CD with guest moieties was not very much large.

Conceptual illustration for interpolymer aggregates of β‐CD polymer with poly(acrylamide)s bearing naphthyl groups substituted on the (a) 1‐ and (b) 2‐positions (see Scheme 1 ).     

Water‐Soluble Carbon Nanotubes by Redox Radical Polymerization

Water‐soluble single‐ and multi‐walled carbon nanotubes (CNTs) were prepared by grafting polyacrylamide chains from the graphitic surface via ceric ion‐induced redox radical polymerization. The reducing functionalities were covalently attached to the tubes by peroxide‐assisted radical reaction. The results showed that polymer chains were grafted onto CNTs by the redox process. The redox radical polymerization initiated by carbon nanotube‐bearing functionalities not only provides a powerful strategy for modifying the carbon nanostructures but also gives us the knowledge of their sidewall chemistry.