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.

     

Amphiphilic Block‐Graft Copolymers with a Degradable Backbone and Polyethylene Glycol Pendant Chains Prepared via Ring‐Opening Polymerization of a Macromonomer

Well‐defined amphiphilic block‐graft copolymers PCL‐b‐[DTC‐co‐(MTC‐mPEG)] with polyethylene glycol methyl ether pendant chains were designed and synthesized. First, monohydroxyl‐terminated macroinitiators PCL‐OH were prepared. Then, ring‐opening copolymerization of 2,2‐dimethyltrimethylene carbonate (DTC) and cyclic carbonate‐terminated PEG (MTC‐mPEG) macromonomer was carried out in the presence of the macroinitiator in bulk to give the target copolymers. All the polymers were characterized by ¹H NMR and gel permeation chromatography (GPC). The polymers have unimodal molecular weight distributions and moderate polydispersity indexes. The amphiphilic block‐graft copolymers self‐assemble in water forming stable micelle solutions with a narrow size distribution.

     

Highly Selective Colorimetric and Fluorometric Probes for Fluoride Ions Based on Nitrobenzofurazan‐containing Polymers

We report on a novel colorimetric and fluorometric chemosensor for fluoride ions based on 4‐(2‐acryloyloxyethylamino)‐7‐nitro‐2,1,3‐benzoxadiazole (NBDAE)‐labeled polymers. Upon gradual addition of fluoride ions (F^–), the green fluorescence emission of NBDAE moieties can be dramatically quenched, accompanied with the distinct colorimetric transition from green to yellow. NBDAE moieties are capable of selectively recognizing F^– ions via hydrogen‐bonding (H‐bonds) interactions at low F^– concentration and subjected to further deprotonation process at high F^– concentration. NBDAE‐labeled polymers in organic solvents possess high selectivity and fluorescence “turn‐off” characteristics toward the sensing of F^– ions with the detection limit down to ≈0.8 µM .

     

Highly Selective Anionic Counterion‐based Fluorescent Sensor for Hg2+ by Grafted Conjugated Polyelectrolytes

Grafted conjugated polyelectrolytes were synthesized for the first time and characterized. The polymers demonstrated properties of a convenient and efficient protocol for creating Hg²⁺ sensors. The unique character of the new material comes from an anionic counterion nature with no external cofactors, and imparts high selectivity and fast detection for mercury ion in a fluorescence probe. The concept may be potentially applied to create new sensors for monitoring other ions.

     

A New Concept for an Alkaline Developable Positive‐Tone Resist: Molecular Resist Utilizing Acid Catalyzed Isomerization from Oxabenzonorbornadiene to Naphthol

A novel positive‐tone molecular resist possessing oxabenzonorbornadiene moiety was developed for electron‐beam (EB) lithography. The synthesized resist material showed relatively high glass transition temperature and readily formed uniform amorphous films on a silicon wafer. The sensitivity of an EB resist was ca. 8 µC · cm⁻² and line and space patterns of 200 nm could be fabricated. The promising feature of the resist materials is that no outgassed products from base matrixes are theoretically produced under the exposure and post‐exposure bake procedure.

     

Probability Distribution Function of the Polymer End‐to‐End Molecule Vector after Retraction and its Application to Step Deformation

The classical Doi‐Edwards model describes the dynamics of polymer strands between entanglements and predicts stress in linear polymers. This contribution considers the dynamics of whole molecules within the same tube picture. The probability distribution function of the end‐to‐end molecule vectors after deformation and retraction was calculated. The second moment of the distribution function coincides with that derived earlier by Doi and Edwards. The damping function shows considerably weaker thinning if the molecule end‐to‐end vector is considered as a Hookean spring. The present model describes one of the possible mechanisms leading to weaker damping exhibiting, e.g., by branched polymers.

     

Sugar-containing polyanions as a self-assembled coating of plasmid/polycation complexes for receptor-mediated gene delivery

Novel poly(ethylene glycol) (PEG) derivatives having both carboxylic acid, and sugar side chains were synthesized. These polymers were used to coat DNA/poly(ethyleneimine) complexes, and effectively protected them against albumin-induced aggregation. They presented carbohydrate moieties on the DNA complex surfaces as a cell-binding ligand, and the galactose-bearing polymer remarkably enhanced the poly(ethyleneimine)-mediated gene transfection on HepG2 cells.

Synthesis of poly(ethylene glycol) derivatives having both carboxylic acid and sugar pendant groups.     

Post‐Functionalization of Polymers via Orthogonal Ligation Chemistry

The establishment of advanced living/controlled polymerization protocols allows for engineering synthetic polymers in a precise fashion. Combining advanced living/controlled polymerization techniques with highly efficient coupling chemistries facilitates quantitative, modular, and orthogonal functionalization of synthetic polymer strands at their chain termini as well as side‐chain functionalization. The review highlights the current status of selected post‐functionalization techniques of polymers via orthogonal ligation chemistries, major characteristics of the specific transformation chemistry, as well as the characterization of the products.

     

Transparent Nonlinear Optical Polymers for All‐Optical Wavelength Converters in Optical Fiber Communications

After synthesizing two chromophores with imine, we prepared acrylic nonlinear optical (NLO) polymers that contained the chromophores for all‐optical wavelength converters in optical fiber communication. The polymers show high d₃₃, 35 pm · V⁻¹, at 1.55 μm (pumping beam), considering their low losses, −3.0 dB · cm⁻¹, at a wavelength of 0.785 μm (near second harmonic signal beam of the pumping beam). This result means that the polymers are good candidates for wavelength converters of an approximately 1.55 μm signal beam.

UV‐vis spectra of NLO chromophores and polymers.     

RAFT Polymerization and Thiol Chemistry: A Complementary Pairing for Implementing Modern Macromolecular Design

Reversible addition fragmentation chain transfer (RAFT) polymerization is one of the most extensively studied reversible deactivation radical polymerization methods for the production of well‐defined polymers. After polymerization, the RAFT agent end‐group can easily be converted into a thiol, opening manifold opportunities for thiol modification reactions. This review is focused both on the introduction of functional end‐groups using well‐established methods, such as thiol‐ene chemistry, as well as on creating bio‐cleavable disulfide linkages via disulfide exchange reactions. We demonstrate that thiol modification is a highly attractive and efficient chemistry for modifying RAFT polymers.

     

The Interaction between Collagen and an Aluminum Tanning Agent

The interaction between collagen and organometallic aluminum complexes was studied. From the analysis of the IR and UV spectra, the viscosity of collagen, and the treated collagen, a possible interaction model of the collagen with the aluminum tanning agent has been found. It indicates that such an aluminum tanning agent could be used as a cleaner tanning agent in leather tanning.

Viscosity curves of the untreated collagen solution (a) and the collagen solution treated with aluminum tanning agent (b).     

Conjugated Microporous Networks on the Basis of 2,3,5,6‐Tetraarylated Diketopyrrolo[3,4‐c]pyrrole

π‐Conjugated microporous networks have been prepared from the tetraarylated diketopyrrolo[3,4‐c]pyrrole unit as a tetrafunctional building block. The reactions are carried out using microwave‐assisted Yamamoto or Sonogashira cross‐coupling. Red insoluble powders are obtained, showing intense fluorescence. The polymer networks exhibit a high gas storage capability, with BET surface areas up to about 500 m² · g⁻¹.

     

A Mechanochemical Approach to Nanocomposites Using Single‐Wall Carbon Nanotubes and Poly(L‐lysine)

A simple method to fabricate polymer nanocomposites with single‐walled carbon nanotubes is reported, in which the nanotubes were reacted with poly(L ‐lysine) by using high‐speed vibration milling. The nanocomposites obtained were characterized by Fourier transform infrared (FT‐IR), UV–Vis spectroscopy, and thermogravimetric methods. The morphology as well as the dispersion of the carbon nanotubes were determined by scanning and transmission electron microscopy.

     

Electrical Conductivity of an Individual Polyaniline Nanotube Synthesized by a Self‐Assembly Method

Camphor sulfonic acid (CSA) doped polyaniline (PANI) nanotubes (175 nm in outer diameter and 120 nm in inner diameter) were synthesized successfully by a self‐assembly method. It is found that the room‐temperature conductivity of an individual PANI nanotube is 30.5 S · cm⁻¹; in particular, the intrinsic resistance of an individual nanotube (30 kΩ) is much smaller than the contact resistance of crossed nanotubes (500 kΩ).

A SEM image of two crossed PANI‐CSA nanotubes and the attached Pt electrodes.     

Water‐Soluble Conjugated Polymers for Fluorescent‐Enzyme Assays

Enzyme assays are receiving more and more research and application interest because of the rapidly increasing demands of clinical diagnosis, environmental analysis, drug discovery, and molecular biology. Water‐soluble light‐harvesting conjugated polymers (CPs) coordinate the action of a large number of absorbing units to afford an amplified fluorescence signal, which makes them useful as optical platforms in highly sensitive chemical and biological sensors. This Feature Article highlights recent developments of water‐soluble CPs for fluorescent assays of enzymes. Different signal transduction mechanisms, such as electron transfer, fluorescence resonance energy transfer (FRET), and aggregation or conformation changes of CPs, are employed in these assays according to the dissimilar nature of enzymes. Potential challenges and future research directions in these approaches based on CPs are also discussed.

     

Synthesis and Optical Properties of Dendronized Porphyrin Polymers

Summary: A novel kind of dendronized porphyrin polymers was synthesized by Sonogashira coupling of diethynyl‐functionalized porphyrin monomers and diiodo‐functionalized macromonomers bearing Fréchet‐type dendrons. The encapsulation of red‐light‐emitting porphyrin‐containing conjugated backbones into dendronized polymers can not only reduce the aggregation of polymer backbones and the self‐quenching of their fluorescence but also endow the porphyrin polymers with good solubility. We also report the optical and electrochemical properties of the porphyrin‐containing dendronized polymers.

Synthesis of a novel kind of dendronized porphyrin polymers by Sonogashira coupling of diethynyl‐functionalized porphyrin monomers and diiodo‐functionalized dendritic macromonomers.     

Synthesis and Characterization of Functional Thienyl‐Phosphine Microporous Polymers for Carbon Dioxide Capture

A novel kind of functional organic microporous polymer is designed by introducing polar organic groups (P=O and P=S) and electron‐rich heterocyclic into the framework to obtain high carbon dioxide capture capacity. The estimated Brunauer–Emmett–Teller (BET) surface areas of these polymers are about 600 m² g⁻¹ and the highest CO₂ uptake is 2.26 mmol g⁻¹ (1.0 bar/273 K). Interestingly, the polymer containing P=O groups shows greater CO₂ capture capacity than that containing P=S groups at the same temperature. In addition, these polymers show high isosteric heats of CO₂ adsorption (28.6 kJ mol⁻¹), which can be competitive with some nitrogen‐rich networks. Therefore, these microporous polymers are promising candidates for carbon dioxide capture.

     

Following Polymer Brush Growth Using the Quartz Crystal Microbalance Technique

Summary: The growth of surface‐initiated poly([2‐(methacryloyloxy)ethyl]trimethylammonium chloride) (pMETAC) brushes by ATRP was monitored by the quartz crystal microbalance technique with dissipation (QCM‐D). The change in mass of the quartz crystals starting from the adsorption of a thiol initiator monolayer through to the growth of the polymer brushes was determined. The use of QCM‐D allowed determination of the kinetics of polymerization from the surface. The technique can be applied to other polymers synthesised from surfaces and allows the study of varying conditions on the polymerization kinetics.

Changes in frequency of a quartz crystal during polymerization.     

Entanglement Transition in Hyperbranched Polyether‐Polyols

Are hyperbranched polymers capable of forming entanglements? This is the central issue of this contribution. Hyperbranched polyglycerol (hbPG) samples with different molecular weights (600–106 000 g · mol⁻¹), narrow polydispersities (1.2–1.8) and high degrees of branching (≈0.6) were prepared by anionic ring‐opening polymerization. The viscoelastic properties of these polymers with respect to molecular architecture and molar mass were investigated. At low molecular weights “classical” scaling behavior between zero shear viscosity and molecular weight can be observed, whereas between 3 000 and 10 000 g · mol⁻¹ a plateau‐like area is found. The results indicate entanglement dynamics when exceeding a critical molar mass ( ≈ 20 000 g · mol⁻¹) due to entangled hyperbranched polyglycerols.