Kinetically Controlled Sequential Growth of Surface‐Grafted Chiral Supramolecular Copolymers

We report a facile strategy to grow supramolecular copolymers on Au surfaces by successively exposing a surface‐anchored monomer to solutions of oppositely charged peptide comonomers. Charge regulation on the active chain end of the polymer sufficiently slows down the kinetics of the self‐assembly process to produce kinetically trapped copolymers at near‐neutral pH. We thereby achieve architectural control at three levels: The β‐sheet sequences direct the polymerization away from the surface, the height of the supramolecular copolymer brushes is well‐controlled by the stepwise nature of the alternating copolymer growth, and 2D spatial resolution is realized by using micropatterned initiating monomers. The programmable nature of the resulting architectures renders this concept attractive for the development of customized biomaterials or chiral interfaces for optoelectronics and sensor applications.     

Consequences of Block Sequence on the Orthogonal Folding of Triblock Copolymers

ABA‐ and BAB‐type triblock copolymers possessing pendant, self‐assembling motifs in the A and B blocks were synthesized, with 2‐ureidopyrimidinone (UPy) and benzene‐1,3,5‐tricarboxamide (BTA) for the A and B block, respectively. They were investigated to assess if and how the polymer’s microstructure influences the self‐assembly behavior of the supramolecular motifs and, as a result, the single‐chain folding process. BAB‐type triblock copolymers were synthesized via atom transfer radical polymerization (ATRP) with molecular weights ranging from 30 to 120 kg mol^?1; the BTA and UPy motifs were attached using a post‐functionalization approach. The ABA‐type triblock copolymers were available from previous work. In highly dilute solutions, both types of triblock copolymers fold into single‐chain polymeric nanoparticles (SCPNs) via thermally induced BTA self‐assembly and photo‐triggered UPy dimerization. Chain collapse induced by intramolecular UPy dimerization was evaluated using size‐exclusion chromatography (SEC). The BTA self‐assembly was monitored by circular dichroism (CD) spectroscopy. The microstructures of SCPNs were visualized by atomic force microscopy (AFM). SEC analysis indicated a more loose packing for the BAB‐type folded nanoparticles than for the ABA‐type ones, which implies that topological differences in the polymer architecture do affect the folding behavior, although only slightly. The facile synthetic protocol developed here provides topologically different triblock architectures and opens up the area for single‐chain folding technology that is applicable in artificial enzymatic systems with compartmentalized domains.     

A novel synthesis of polymer brush on multiwall carbon nanotubes bearing terminal monomeric unit

A novel approach to fabricate polymer brushes on the surface of carbon nanotubes (CNTs) is proposed. Carboxyl groups on the surface of chemically oxidized CNTs were reacted with hexamethylene diisocyanate, followed by a reaction with methacrylamide to give terminal vinyl groups‐functionalized CNTs, so called “CNT‐mer.” The synthetic procedure was investigated step‐by‐step and the synthesized CNT‐mer was used to grow polystyrene (PS) from CNTs by a simple in situ polymerization in the presence of a thermal initiator. By employing ¹H NMR, X‐ray photoelectron spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and light scattering, the experimental results were verified. Using this approach, 45% PS with respect to CNTs are grafted on the surface of CNTs with about 4.0 nm thickness. This novel technique would provide a facile route to prepare tailor‐made polymer brushes on the surface of CNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6394–6401, 2006     

Limitations of cyclodextrin‐mediated RAFT homopolymerization and block copolymer formation

The design and synthesis of a new hydrophobic monomer, that is, 4‐(tert‐butyl)phenyl 6‐acrylamidohexanoate (TBP‐AA‐HO) and its ability to form supramolecular host/guest complexes with β‐cyclodextrin (CD) is described. The aqueous CD‐mediated reversible addition fragmentation chain transfer (RAFT) polymerization affords molecular masses up to 8600 g mol^?1 with polydispersities between 1.2 and 1.4. The surprisingly low molecular weights for higher monomer/chain transfer agent (CTA) ratios are investigated by comparing results obtained from free radical and RAFT radical polymerization in aqueous and organic media. The results indicate a steric hindrance caused by attached CD molecules on the growing polymer chain leading to stagnation of the polymerization process due to a restricted accessibility of the reactive chain end. This hypothesis is supported by matrix‐assisted laser desorption/ionization time of flight mass spectrometry. Furthermore, the CD‐mediated synthesis of amphiphilic diblock copolymers in variable aqueous media is described. Hydrophilic poly(N,N‐dimethylacrylamide) macro‐CTAs with different molecular weights are used to polymerize TBP‐AA‐HO at 50 °C. The diblock copolymers are analyzed by ¹H‐nuclear magnetic resonance spectroscopy and size exclusion chromatography. The results confirm the polymer structure and reveal similar limitations of chain growth as observed for the CD‐mediated homopolymerization with a limit of 7000 g mol^?1 for efficient chain extension. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2504–2517     

Phototriggered Supramolecular Polymerization

Photo‐initiated supramolecular polymerization of a naphthalenediimide (NDI‐1) derivative containing an ortho‐nitrobenzyl (ONB)‐protected amide group is demonstrated. In a hydrocarbon solvent (methylcyclohexane), it remains as monomer. Upon photo‐irradiation, deprotection of the ONB group produces NDI‐2 with a free amide group, which drives supramolecular polymerization by self‐complementary H‐bonding between the amide groups, leading to gelation. The polymerization rate can be controlled by tuning the energy of the light source. During photopolymerization, a gradual increase in hydrodynamic radius and viscosity is noticed. More interestingly, the morphology of the supramolecular polymer of NDI‐2, produced by photo‐irradiation, was a spherulite, which is in sharp contrast with the fibrillar morphology of NDI‐2 polymer, when assembled spontaneously without a phototrigger. This is ascribed to the ability of the ONB‐caged pro‐monomer (NDI‐1) to act as a chain‐stopper by forming a H‐bonded complex with the active monomer during the growth of the supramolecular polymer under photo‐irradiation.     

A strategy for synthesis of ion‐bonded amphiphilic miktoarm star copolymers via supramolecular macro‐RAFT agent

Amphiphilic supramolecular miktoarm star copolymers linked by ionic bonds with controlled molecular weight and low polydispersity have been successfully synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using an ion‐bonded macromolecular RAFT agent (macro‐RAFT agent). Firstly, a new tetrafunctional initiator, dimethyl 4,6‐bis(bromomethyl)‐isophthalate, was synthesized and used as an initiator for atom transfer radical polymerization (ATRP) of styrene to form polystyrene (PSt) containing two ester groups at the middle of polymer chain. Then, the ester groups were converted into tertiary amino groups and the ion‐bonded supramolecular macro‐RAFT agent was obtained through the interaction between the tertiary amino group and 2‐dodecylsulfanylthiocarbonylsulfanyl‐2‐methyl propionic acid (DMP). Finally, ion‐bonded amphiphilic miktoarm star copolymer, (PSt)₂‐poly(N‐isopropyl‐acrylamide)₂, was prepared by RAFT polymerization of N‐isopropylacrylamide (NIPAM) in the presence of the supramolecular macro‐RAFT agent. The polymerization kinetics was investigated and the molecular weight and the architecture of the resulting star polymers were characterized by means of ¹H‐NMR, FTIR, and GPC techniques. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5805–5815, 2008     

Playing LEGO with macromolecules: Design,synthesis, and self‐organization with metal complexes

Several synthetic strategies for the incorporation of supramolecular binding units into polymers are described. Specifically, terpyridine ligands have been introduced into polymers in such a way that they are distributed either randomly throughout the polymer backbone or at the chain end(s). Two terpyridine ligands form octahedral complexes with a variety of transition‐metal ions, each having different properties. Some general statements regarding metal complex stability are presented as well as a special case representing the selective construction of heteroleptic terpyridine complexes. This leads to a kind of LEGO system for connecting and disconnecting the polymer blocks via metal complexes. Metallo‐supramolecular block copolymers, graft copolymers, and chain‐extended polymers can be designed and prepared with the principles described. Once the design parameters have been derived, thorough control over the final material and its properties can be gained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1413–1427, 2003     

Synthesis and characterization of water‐dispersible,superparamagnetic single‐wall carbon nanotubes decorated with iron oxide nanoparticles and well‐defined chelating diblock copolymers

A novel approach for the fabrication of magneto‐active carbon nanotubes (CNTs) stabilized in aqueous media, involving the combination of carboxylated single‐wall carbon nanotubes (SWCNTs) with a new class of methacrylate‐based chelating diblock copolymers, is described. More precisely, a well‐defined diblock copolymer consisting of hexa(ethylene glycol) methyl ether methacrylate (hydrophilic and thermo‐responsive) and 2‐(acetoacetoxy)ethyl methacrylate (hydrophobic and metal‐chelating) synthesized by reversible addition‐fragmentation chain transfer polymerization has been used to prepare polymer‐coated magneto‐active SWCNTs decorated with iron oxide nanoparticles. Further to the characterization of the compositional and thermal properties using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction spectroscopy and thermal gravimetric analysis, assessment of the magnetic characteristics by vibrational sample magnetometry disclosed superparamagnetic behavior at room temperature. The latter, combined with the thermo‐responsive properties of the polymeric coating and the unique, inherent properties of the carbon nanotubes may allow for their future exploitation in the biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1389–1396, 2011     

Interfacial living radical copolymerization of oil‐ and water‐soluble comonomers to form composite polymer capsules

The suspension copolymerization of methyl methacrylate with hydroxy‐functional poly(ethylene glycol) monomethacrylate (PEGMA) by atom transfer radical polymerization (ATRP) yielded soluble, controlled‐molecular‐weight amphiphilic copolymers (weight‐average molecular weight/number‐average molecular weight <1.3). Despite extensive partitioning of PEGMA into the water phase, copolymers containing up to 24 mol % PEGMA were formed in the oil phase, from comonomer feeds containing 30 mol % PEGMA. Conversions by suspension polymerization were comparable to those obtained by solution polymerization, at over 70%. Suspension copolymers with high PEGMA contents contained high‐molecular‐weight polymer formed by uncontrolled polymerization, unless poly(vinyl pyrrolidone) was added to displace the growing polymer from the interface. The addition of diethylene glycol dimethacrylate gave capsules at 17 mol % PEGMA with ATRP, whereas conventional free‐radical polymerization required 24 mol % PEGMA to form capsules. The lower PEGMA level required for capsule formation with ATRP was attributed to the lower rates of propagation and crosslinking and to improved incorporation of PEGMA into the final gels. Suspension ATRP with 24 mol % PEGMA in the feed gave two‐layer capsule walls consisting of an inner layer visible by transmission electron microscopy and an outer layer visible by both transmission electron microscopy and environmental scanning electron microscopy, which indicated a compositional gradient across the capsule wall. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 156–171, 2006     

Supramolecular complexes of poly(3‐Hexylthiophene)‐block (and random)‐poly[3‐(2‐(6‐carboxyhexyl)methyl)thiophene] copolymers with perylene bisimide

Block and random copolymers of poly(3‐hexylthiophene) and poly[3‐(2‐(6‐carboxyhexyl)methyl)thiophene] with side‐chain carboxylic functionality ((P3HT‐b‐P3COOH) and (P3HT‐r‐P3COOH) were developed by Grignard Metathesis (GRIM) polymerization. The carboxylic functionality was introduced in the side chain via the oxazoline route. Both the block and random polythiophene copolymers were complexed with pyridine functionalized perylene bisimide to obtain supramolecular block and random polymer complexes. The complex formation in both systems was confirmed by ¹H NMR, WXRD and SAXS studies. An expansion of d spacing upon complex formation was observed in both the block and random copolymer, which could be traced by WXRD. Hole and electron mobilities measured for the supramolecular complexes indicated values which were higher by an order of magnitude for the supramolecular block complex (μ_h ≈ 2.9 × 10⁻⁴ cm²/Vs; μ_e ≈ 3.1 × 10⁻⁶ cm²/Vs) as compared to the random (μ_h ≈ 1.4 × 10⁻⁵ cm²/Vs; μ_e ≈ 4.7 × 10⁻⁷ cm²/Vs) copolymer. These results are indicative of the higher degree of disorder prevailing in the films of random copolymer system compared to the block copolymer. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1574–1583     

Orthogonally Self‐Assembled Multifunctional Block Copolymers

We report the synthesis of telechelic poly(norbornene) and poly(cyclooctene) homopolymers by ring‐opening metathesis polymerization (ROMP) and their subsequent functionalization and block copolymer formation based on noncovalent interactions. Whereas all the poly(norbornene)s contain either a metal complex or a hydrogen‐bonding moiety along the polymer side‐chains, together with a single hydrogen‐bonding‐based molecular recognition moiety at one terminal end of the polymer chain. These homopolymers allow for the formation of side‐chain‐functionalized AB and ABA block copolymers through self‐assembly. The orthogonal natures of all side‐ and main‐chain self‐assembly events were demonstrated by ¹H NMR spectroscopy and isothermal titration calorimetry. The resulting fully functionalized block copolymers are the first copolymers combining both side‐ and main‐chain self‐assembly, thereby providing a high degree of control over copolymer functionalization and architecture and bringing synthetic materials one step closer to the dynamic self‐assembly structures found in nature.     

Synthesis of IONP's decorated graft copolymers and study of their magnetic force–induced wastewater treatment

Our work is focused on facile synthesis and modification of amylopectin‐grafted block copolymers by using reversible addition?fragmentation chain transfer (RAFT) polymerization technique. This technique yields polymers with controlled molecular weight and low polydispersity indexes and is feasible with a wide range of monomers. Five different grades of amylopectin‐grafted polymethacrylic acid and polyacrylamide block copolymers have been synthesized via RAFT, by varying the amount of acrylamide employing amylopectin‐based macro chain transfer agent. Graft copolymers have been upgraded as smart responsive graft copolymers, through the incorporation of iron oxide nanoparticles (IONPs) via condensation reaction. The polymeric materials have been extensively characterized by energy‐dispersive X‐ray analysis, Fourier transform infrared spectroscopy, proton magnetic resonance spectroscopy, scanning electron microscopy, ultraviolet‐visible spectroscopy, gel permeation chromatography, transmission electron microscopy, thermogravimetric analysis, and X‐ray diffraction analysis. Normal and responsive graft copolymers have been studied for removal of model contaminant (kaolin), and responsive graft copolymers have been used to remove methylene blue dye (without using any adsorbent) from water by applying external magnetic field. The upgraded block copolymers have shown best performance in wastewater treatment.     

Styrene‐vinyl pyridine diblock copolymers: Achieving high molecular weights by the combination of anionic and reversible addition–fragmentation chain transfer polymerizations

Anionic and reversible addition–fragmentation chain transfer (RAFT) polymerizations were combined for the preparation of high molecular weight (MW) amphiphilic diblock copolymers based on the hydrophobic styrene (Sty) and the more polar 2‐vinyl pyridine (2VPy) or 4‐vinyl pyridine (4VPy). In particular, four amphiphilic Sty‐VPy diblock copolymers with MWs up to 271,000 g mol^–1 were prepared. For the polymer synthesis, first, living anionic polymerization of Sty using sec‐butyl‐lithium as initiator in tetrahydrofuran at ?70 °C, followed by termination with ethylene oxide were employed for the preparation of OH‐functionalized homopolyStys. Subsequently, a modification of the OH‐terminal group was performed by the attachment of a 4‐cyanopentanoic acid dithiobenzoate chain transfer agent (CTA) group, giving a polySty macroRAFT CTA, which was extended with 2VPy or 4VPy units using RAFT polymerization. Thus, the prepared diblock copolymers comprised a first block which was near‐monodisperse in size, and a second more heterogeneous block. All diblock copolymers were characterized in terms of their MWs and compositions by gel permeation chromatography and ¹H NMR spectroscopy, respectively, giving results close to the theoretically expected values. Films cast from chloroform solutions of the diblock copolymers were investigated in terms of their bulk morphologies using transmission electron microscopy, which indicated that the minority block consistently formed the discontinuous microphase, spherical or cylindrical. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Effect of selected structural parameters of styrene–butadiene block copolymers on their compatibilization efficiency in polystyrene/polybutadiene blends

The effects of the block length and block number of linear styrene–butadiene (S–B) block copolymers on their compatibilization efficiency in blending polystyrene with polybutadiene were studied. For this purpose, two sets of model S–B copolymers and both homopolymers were prepared by anionic polymerization. Diblocks, triblocks, or pentablocks of S–B copolymers were blended with these homopolymers, and the structures and some end‐use properties of the blends were determined. The supramolecular structure (determined by small‐angle X‐ray scattering), morphology (determined by transmission and scanning electron microscopy), and stress‐transfer characteristics (impact and tensile strengths) of the blends were chosen as criteria for the compatibilization efficiency of the copolymers used. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2612–2623, 2002     

Synthesis of Polymers Containing Potassium Acyltrifluoroborates (KATs) and Post‐polymerization Ligation and Conjugation

We report the synthesis of monomers for atom‐transfer radical polymerization (ATRP) and a reversible addition‐fragmentation chain transfer (RAFT) agent bearing trifluoroborate iminiums (TIMs), which are quantitatively converted into potassium acyltrifluoroborates (KATs) after polymerization. The resulting KAT‐containing polymers are suitable for rapid amide‐forming ligations for both post‐polymerization modification and polymer conjugation. The polymer conjugation occurs rapidly, even under dilute (micromolar) aqueous conditions at ambient temperatures, thereby enabling the synthesis of a variety of linear and star‐shaped block copolymers. In addition, we applied post‐polymerization modification to the covalent linking of a photocaged cyclic antibiotic (gramicidin S) to the side chains of the KAT‐containing copolymer. Cellular assays revealed that the polymer–antibiotic conjugate is biocompatible and provides efficient light‐controlled release of the antibiotic on demand.     

Polyferrocenylsilanes: Metal‐Containing Polymers for Materials Science,Self‐Assembly and Nanostructure Applications

Polyferrocenylsilanes represent a recently established, readily accessible class of transition metal‐containing macromolecules consisting of alternating ferrocene and organosilane units. High molecular weight, soluble samples of these materials were first prepared in the early 1990's by thermal ring‐opening polymerization (ROP) of silicon‐bridged [1]ferrocenophanes ([1]silaferrocenophanes). More recently living anionic and transition metal‐catalyzed ROP methodologies have been developed, which permit unprecedented access to controlled polymer architectures (e.g. block copolymers) with transition metals in the main chain. Polyferrocenylsilane homopolymers and block copolymers offer exciting opportunities in materials and supramolecular science and for nanostructure applications. In this article some recent research areas are discussed which illustrate the broad scope of these interesting new materials.     

Photocontrolled Synthesis of n‐Type Conjugated Polymers

Current approaches to synthesize π‐conjugated polymers (CPs) are dominated by thermally driven, transition‐metal‐mediated reactions. Herein we show that electron‐deficient Grignard monomers readily polymerize under visible‐light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain‐growth process; correspondingly, chain extension produces all‐conjugated n‐type block copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor–acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n‐type CPs without the need for transition‐metal catalysis.     

Chitosan‐Functionalized Carbon Nanotubes as Support for the High Dispersion of PtRu Nanoparticles and their Electrocatalytic Oxidation of Methanol

Carbon nanotubes (CNTs) were non‐covalently functionalized with chitosan (Chit) and then employed as the support for PtRu nanoparticles. The functionalization was carried out at room temperature without the use of corrosive acids, thereby preserving the integrity and the electronic conductivity of the CNTs. Transmission electron microscopy reveals that PtRu nanoparticles were highly dispersed on the surface of Chit‐functionalized CNTs (CNT‐Chit) with small particle‐size. Cyclic voltammetry studies indicated that the PtRu nanoparticle/CNT‐Chit nanohybrids have a higher electrochemical surface area, electrocatalytic performance, and stability towards methanol oxidation compared to PtRu nanoparticles supported on the pristine CNTs.     

Dynamically Controllable Emission of Polymer Nanofibers: Electrofluorescence Chromism and Polarized Emission of Polycarbazole Derivatives

Electrochemical polymerization of a series of N‐alkyl‐2,7‐di(2‐thienyl)carbazoles in acetonitrile was performed to obtain conjugated polymers with fluorescence. Scanning electron and atomic force microscopies revealed that the surface morphology of the polymer films significantly depends on the alkyl chain lengths of the polymers. Particularly, a homopolymer bearing hexyl groups and copolymers with an average alkyl chain length of six carbon atoms show nanofiber morphology. The polymer nanofibers were stacked on a substrate electrode. The fluorescence of the polymer nanofiber film was tunable with application of voltage, with good repeatability. The X‐ray diffraction pattern of the fibers showed the structural order. The polymer nanofibers thus prepared showed an electrochemically driven change in polarized photoluminescence.     

Preparation of nanoparticles of double‐hydrophilic PEO‐PHEMA block copolymers by AGET ATRP in inverse miniemulsion

Atom transfer radical polymerization with activators generated by electron transfer initiating/catalytic system (AGET ATRP) of 2‐hydroxyethyl methacrylate (HEMA) was carried out in inverse miniemulsion. Water‐soluble ascorbic acid as a reducing agent and mono‐ and difunctional poly(ethylene oxide)‐based bromoisobutyrate (PEO‐Br) as a macroinitiator were used in the presence of CuBr₂/tris[(2‐pyridyl)methyl]amine (TPMA) and CuCl₂/TPMA complexes. The use of poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide) as a polymer surfactant resulted in the formation of stable HEMA cyclohexane inverse dispersion and PHEMA colloidal particles. All polymerizations were well‐controlled, allowing for the preparation of well‐defined PEO‐PHEMA and PHEMA‐PEO‐PHEMA block copolymers with relatively high molecular weight (DP > 200) and narrow molecular weight distribution (M_w/M_n < 1.3). These block copolymers self‐assembled to form micellar nanoparticles being 10–20 nm in diameter with uniform size distribution, and aggregation number of ～10 confirmed by atomic force microscopy and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4764–4772, 2007