Reduced Graphene Oxide/Poly(3‐hexylthiophene) Supramolecular Composites

Poly(3‐hexylthiophene) (P3HT) supramolecular structures are fabricated on P3HT‐dispersed reduced graphene oxide (RGO) monolayers and surfactant‐free RGO monolayers. P3HT is able to disperse RGO in hot anisole/N,N‐dimethylformamide solvents, and forms nanowires on RGO surfaces through a RGO induced crystallization process. The TEM and AFM investigation of the resultant P3HT/RGO composites shows that P3HT nanowires grow from RGO, and connect individual RGO monolayers. Raman spectroscopy confirms the interaction between P3HT and RGO, which allows the manipulation of the RGO electrical properties. Such a bottom‐up approach provides interesting graphene‐based composites for nanometer‐scale electronics.

     

Poly(cyclic imino ether)s Beyond 2‐Substituted‐2‐oxazolines

2‐Oxazolines (2‐OZO) are 5‐membered cyclic imino ethers whose cationic ring‐opening polymerization (CROP) mechanism and resulting polymer properties are extensively studied. However, also 6‐ and 7‐membered cyclic imino ethers can be polymerized via CROP. Together with the much less studied 4‐ and 5‐substituted main‐chain chiral poly(2‐oxazoline)s (P‐2‐OZO), these compounds are interesting monomers to enhance the versatility of (co)poly(cyclic imino ether)s. To emphasize the potential of such alternative cyclic imino ether monomers, we provide an overview on the polymerizations of 2‐oxazine (2‐OZI) and chiral 4‐ and 5‐substituted 2‐OZO as well as of selected properties of the resulting polymers. In addition, the hydrolysis of these polymers into the corresponding poly(alkylene imine)s will be addressed.

     

Synthesis and Characterization of a Block Copolymer Containing Regioregular Poly(3‐hexylthiophene) and Poly(γ‐benzyl‐L‐glutamate)

Poly(3‐hexylthiophene)‐b‐poly(γ‐benzyl‐L ‐glutamate) (P3HT‐b‐PBLG) rod–rod diblock copolymer was synthesized by a ring‐opening polymerization of γ‐benzyl‐L ‐glutamate‐N‐carboxyanhydride using a benzylamine‐terminated regioregular P3HT macroinitiator. The opto‐electronic properties of the diblock copolymer have been investigated. The P3HT precursor and the P3HT‐b‐PBLG have similar UV–Vis spectra both in solution and solid state, indicating that the presence of PBLG block does not decrease the effective conjugation length of the semiconducting polythiophene segment. The copolymer displays solvatochromic behavior in THF/water mixtures. The morphology of the diblock copolymer depends upon the solvent used for film casting and annealing results in morphological changes for both films deposited from chloroform and trichlorobenzene.

     

Advancing the Solid State Properties of Metallo‐Supramolecular Materials: Poly(ε‐caprolactone) Modified π‐Conjugated Bis(terpyridine)s and their Zn(II) Based Metallo‐Polymers

A set of rigid π‐conjugated bis(terpyridine) macroligands with poly(ε‐caprolactone) (pCL) on their side chains was synthesized and investigated. The introduced pCL chains gave rise to enhanced processability and film‐forming properties of the materials. Blue photoluminescence with high quantum yields was observed in dilute solution and in the solid state, indicating that intermolecular aggregation of the π‐conjugated systems was effectively suppressed. The macroligands were further used for coordination with zinc(II) ions leading to new metallo‐polymers with high solubility, improved film‐forming behavior and promising photophysical properties with respect to potential OLED applications.

     

Biotin α‐End‐Functionalized Gradient Glycopolymers Synthesized by RAFT Copolymerization

Biotinylated gradient glycopolymers have been synthesized via RAFT copolymerization of an acrylamide derivative of galactose with N‐acryloylmorpholine in the presence of a biotin CTA. The polymerization was controlled with a linear increase in molecular weights up to 80% conversion. Copolymer chains have a gradient microstructure with an increasing proportion of galactose units towards the ω chain end. The presence of the biotin ligand at the α end of the chains was confirmed by ¹H NMR and MALDI‐ToF MS. This strategy based on the use of a biotin‐CTA instead of a post‐polymerization labelling of the chains resulted in a high percentage of α‐functionalized chains (92–95%). Such α‐end‐functionalized glycopolymer chains may interact with streptavidin‐modified surfaces.

     

New Poly(propylene glycol)‐ and Poly(ethylene glycol)‐Based Polymer Gelators with L‐Lysine

Summary: New polymer gelators consisting of poly(propylene glycol) or poly(ethylene glycol) and L ‐lysine‐based low‐molecular‐weight gelators have been developed. These polymer gelators were synthesized according to a simple procedure with high reaction yield, and formed organogels in many organic solvents. The organogelation mechanism was proposed from the transmission electron microscopy and FTIR spectroscopy studies.

Structures of the polymer gelators synthesized here.     

Dual Self‐Assembling Polycondensation of p‐Acetoxybenzoic Acid and p‐Acetamidobenzoic Acid

The dual self‐assembling polycondensation of p‐acetoxybenzoic acid (ABA) and p‐acetamidobenzoic acid in Therm S 800 was examined at 300 °C. Needle‐like crystals and lath‐like crystals were formed simultaneously through reaction‐induced crystallization of oligomers at a molar ratio of 30–50 mol‐% ABA in the feed. The needle‐like crystals comprised more p‐oxybenzoyl units, whereas the lath‐like ones contained higher amounts of p‐benzamide moieties.

     

Synthesis of CdSe–Poly(N‐vinylcarbazole) Nanocomposite by Atom Transfer Radical Polymerization for Potential Optoelectronic Applications

A hybrid inorganic–polymer nanocomposite using CdSe nanocrystals with high electron mobility has been successfully synthesized by atom transfer radical polymerization (ATRP). First the hydroxyl‐coated CdSe nanoparticles (i.e., CdSe–OH) were prepared via a wet chemical route. A polymerization initiator was then prepared for ATRP of N‐vinylcarbazole. FT‐IR, ¹H NMR, and XRD analyses confirmed the successful synthesis of CdSe–poly(N‐vinylcarbazole) (PVK) nanohybrid. UV–Vis spectra and photoluminescence data revealed that grafting of PVK onto the surface of CdSe nanocrystals would reduce the band gap of PVK and cause the red shift of emission peak. TEM and SEM micrographs exhibited CdSe nanoparticles that were well‐coated with PVK polymer.

     

A Novel Poly(aryleneethynylene) with Tetrathiafulvalene (TTF) Side Chains: Synthesis,Self‐Assembly,and Electroactive Property

A novel poly(aryleneethynylene), in which the main chain and the tetrathiafulvalene (TTF) side chains are coplanar, has been prepared and characterized. The polymer can self‐assemble in tetrahydrofuran (THF) and the π‐extended coplanar backbones adopt good face‐to‐face stacking, which is confirmed by X‐ray diffraction (XRD) analysis. Cyclic voltammetry has revealed that the polymer has reversible electroactive properties. The optical bandgap deduced by UV‐vis absorption spectroscopy and the electrochemical bandgap are 2.03 and 2.14 eV. The conductivities of the powder and the realigning solid of the polymer are 6 × 10⁻⁸ and 4 × 10⁻⁶ S cm⁻¹.

     

Laser Single Pulse Initiated RAFT Polymerization for Assessing Chain‐Length Dependent Radical Termination Kinetics

Summary: A novel method combining RAFT polymerization with pulsed‐laser initiation for determining chain‐length dependent termination rate coefficients, k_t, is presented. Degenerative chain‐transfer in RAFT enables single‐pulse pulsed‐laser polymerization (SP‐PLP) traces to be measured on systems with a narrow radical distribution that remains essentially unchanged during the experiment. SP‐PLP‐RAFT experiments at different polymerization times allow for determining k_t as a function of chain length via classical kinetics assuming chain‐length independent k_t.

Single‐pulse pulsed‐laser polymerization trace for BMPT‐mediated RAFT polymerization of butyl acrylate.     

Poly(diindenonaphthalene) and Poly(indenofluorene) – Tuning the Absorption Properties of Low Bandgap Cross‐Conjugated Polymers

Summary: Semiconducting polymers with moderate HOMO–LUMO energy gaps between 1.5 and 2.0 eV are of increasing attraction as donor components of bulk heterojunction‐type organic solar cells. The synthesis and characterization of a novel cross‐conjugated, aromatic polymer, poly(diindenonaphthalene) PDIN, with a HOMO‐LUMO gap of ca. 1.6 eV (λ_max: 724 nm) in comparison to poly(indenofluorene) PIF, a previously described, structurally related polymer, is presented. The replacement of the central benzene ring of PIF by a naphthalene moiety in PDIN leads to an increase of the optical bandgap energy of ca. 0.16 eV.

Chemical structure of PIF and PDIN.     

One‐Step Synthesis and Size Control of Dendrimer‐Protected Gold Nanoparticles: A Heat‐Treatment‐Based Strategy

Dendrimer‐protected gold nanoparticles have been facilely obtained by heating an aqueous solution containing third‐generation poly(propyleneimine) dendrimers and HAuCl₄ without the additional step of introducing other reducing agents. Transmission electron microscopy (TEM) and UV‐vis data indicate the size, the nucleation, and growth kinetics of gold nanoparticles thus formed, which can be tuned by changing the initial molar ratio of dendrimer to gold.

The formation of dendrimer–gold nanoparticles by the heat treatment of an aqueous solution containing third‐generation poly(propyleneimine) dendrimers and HAuCl₄.     

Highly Extensible Bio‐Nanocomposite Fibers

Here, we show that a poly(ethylene oxide) polymer can be physically cross‐linked with silicate nanoparticles (Laponite) to yield highly extensible, bio‐nanocomposite fibers that, upon pulling, stretch to extreme lengths and crystallize polymer chains. We find that both, nanometer structures and mechanical properties of the fibers respond to mechanical deformation by exhibiting strain‐induced crystallization and high elongation. We explore the structural characteristics using X‐ray scattering and the mechanical properties of the dried fibers made from hydrogels in order to determine feasibility for eventual biomedical use and to map out directions for further materials development.

     

Living Cationic Polymerizations Utilizing an Automated Synthesizer: High‐Throughput Synthesis of Polyoxazolines

Living cationic ring‐opening polymerizations of 2‐ethyl‐2‐oxazoline and purification of the resulting polymers were performed utilizing an automated synthesizer. Eight polymers (500 mg scale) as well as 40 polymers (150 mg scale) were synthesized in parallel to investigate the reproducibility and the living character of the polymerizations. The poly(2‐ethyl‐2‐oxazoline)s obtained such were characterized by means of ¹H NMR spectroscopy, MALDI‐TOF mass spectrometry and online gel permeation chromatography.

     

A Cationic Water‐Soluble Poly(p‐phenylenevinylene) Derivative: Highly Sensitive Biosensor for Iron‐Sulfur Protein Detection

Summary: A new water‐soluble cationic ammonium‐functionalized poly(p‐phenylenevinylene) (PPV‐NEtMe) was successfully synthesized and exhibited high sensitivity (K_sv = 6.9 × 10⁷ M ⁻¹) on rubredoxin, a type of anionic iron‐sulfur (Fe‐S) proteins. Further investigation showed that the biosensitivity of the cationic conjugated polymer is strongly dependent on the nature of the buffer solution and the concentration of the conjugated polymer used in the analyses.

The schematic diagram of anionic rubredoxin detected by PPV‐NEtMe.     

Construction of a Hexameric Zn(II)‐metallomacrocycle and its Photo‐ and Electroluminescence Properties: [Zn6(O‐hexyl‐3,5‐bis(2,2′:6′,2″‐terpyridine)phenol)6(BF4)12]

Summary: An O‐hexyl‐3,5‐bis(terpyridine)phenol ligand has been synthesized and transformed into a hexagonal Zn(II)‐metallomacrocycle by a facile self‐assembly procedure capitalizing on terpyridine‐Zn(II)‐terpyridine connectivity. The structural composition was confirmed by NMR and mass spectral techniques; photo‐ and electroluminescence properties were also investigated. The OLED device shows green electroluminescent emission at 515 nm with a maximum luminance of 39 cd · m⁻² and maximum efficiency of 0.16 cd · A⁻¹.

Structure and electroluminescent properties of the metallomacrocycle investigated.     

Poly(p‐phenylene ethynylene) Incorporating Sterically Enshrouding m‐Terphenyl Oxacyclophane Canopies

A sterically encumbered m‐terphenyl oxacyclophane substituted with two aryl iodide substituents has been prepared as a versatile monomer for the preparation of π‐conjugated polymers. The monomer has been used to prepare a poly(p‐phenylene ethynylene) derivative (P1) incorporating oxacyclophane units as canopies that shield one side of the π‐system from inter‐chain interactions. The photophysical properties of P1 in dilute solution compare well to those of a poly(p‐phenylene ethynylene) derivative (P2) that lacks the canopy. The presence of the steric canopy leads to a diminished inter‐chain interaction in the solid state and enhances the kinetic response of P1 to vapors of nitro‐organics such as TNT, presumably by increasing the permeability of P1 to these analytes over that of P2.

     

RAFT Inverse Miniemulsion Polymerization of Acrylamide

RAFT inverse miniemulsion polymerization is demonstrated for the first time as an alternate way to synthesize hydrophilic polymer latexes. The kinetic behavior of inverse RAFT miniemulsion polymerization of acrylamide is similar to that observed in aqueous RAFT solution polymerization. A water‐soluble initiator provides better control than a lipophilic initiator in inverse RAFT miniemulsion polymerization under the conditions used here.