Synthesis and conjugation of a triiodohydroxylamine for the preparation of highly X‐ray opaque poly(ε‐caprolactone) materials

To address a need for highly X‐ray opaque biodegradable materials, a series of poly(ε‐caprolactone) derivatives were prepared using oxime post‐polymerization modification to conjugate two different iodinated hydroxylamines. These materials were synthesized with up to 32 wt. % iodine content and demonstrated improved X‐ray contrast relative to both the ketone precursors and previously reported monoiodinated materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 787–793     

Synthesis and morphology investigations of a novel alkyne‐functionalized diblock copolymer

We reported the synthesis and morphology of a novel alkyne‐functionalized diblock copolymer (di‐BCP) poly(methyl methacrylate‐random‐propargyl methacrylate)‐block‐poly(4‐bromostyrene). The di‐BCPs were synthesized by atom transfer radical polymerization and postpolymerization deprotection, with good control over molecular weight and polydispersity index. Microphase separation in bulk di‐BCPs was confirmed by thermal analysis, small‐angle X‐ray scattering, and transmission electron microscopy. Microphase‐separated morphologies were also observed in thin films, and the orientation of the microdomains can be conveniently controlled by annealing under different solvents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis of bithiazole‐based crystalline polymers via palladium‐catalyzed direct CH arylation

Palladium‐catalyzed direct arylation polycondensation afforded a bithiazole‐based homopolymer and donor–acceptor (D–A)‐type copolymers where the bithiazole unit served as an acceptor unit. The results of polymerization strongly depended on the solubility of the polymers; long alkyl chain substituents were required for the formation of high‐molecular‐weight polymers in high yields owing to low solubility of the bithiazole‐based polymers. X‐ray diffraction studies revealed that the obtained polymers were highly crystalline. In particular, a well‐ordered lamellar structure was observed in the D–A‐type copolymer with flexible alkyl chains after thermal annealing, presumably owing to the combination of interchain interactions between the bithiazole units and the electrostatic D–A interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1396–1402     

Iodinated polyesters as a versatile platform for radiopaque biomaterials

The design of polymeric biomaterials with long‐lasting X‐ray contrast could advance safe and effective implants and contrast agents. Herein, a new set of wholly aliphatic, iodinated polyesters are synthesized and evaluated as high‐contrast biomaterials and nanoparticle contrast agents for general computed tomography imaging. A single iodinated monomer is used to synthesize a variety of aliphatic polyesters with tunable thermal and mechanical properties. These iodinated polyesters are end‐functionalized with a photocurable methacrylate group, which allows easy processability. The resulting materials exhibit no cytotoxicity and are radiopaque, containing over 40% iodine by weight after processing. The polymers can be formulated into lipid–polymer hybrid nanoparticles using a modified nanoprecipitation method. Initial studies indicate that these nanoparticles show good continual contrast over 60 minutes with no uptake into the kidneys. The work presented here illustrates a novel platform for iodinated polyesters that exhibit high radiopacity and processability, low cost, and no cytotoxicity. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2171–2177     

Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. I. Crystalline polymer‐solvent compound formation for poly(9,9‐dioctylfluorene)

Polymer‐solvent compound formation, occurring via co‐crystallization of polymer chains and selected small‐molecular species, is demonstrated for the conjugated polymer poly(9,9‐dioctylfluorene) (PFO) and a range of organic solvents. The resulting crystallization and gelation processes in PFO solutions are studied by differential scanning calorimetry, with X‐ray diffraction providing additional information on the resulting microstructure. It is shown that PFO‐solvent compounds comprise an ultra‐regular molecular‐level arrangement of the semiconducting polymer host and small‐molecular solvent guest. Crystals form following adoption of the planar‐zigzag β‐phase chain conformation, which, due to its geometry, creates periodic cavities that accommodate the ordered inclusion of solvent molecules of matching volume. The findings are formalized in terms of nonequilibrium temperature–composition phase diagrams. The potential applications of these compounds and the new functionalities that they might enable are also discussed. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1481–1491     

Postpolymerization modification of poly(pentafluorophenyl methacrylate): Synthesis of a diverse water‐soluble polymer library

This article explores the feasibility of poly(pentafluorophenyl methacrylate) (PPFMA) prepared by reversible addition fragmentation chain transfer (RAFT) polymerization as a platform for the preparation of diverse libraries of functional polymers via postpolymerization modification with primary amines. Experiments with a broad range of functional amines and PPFMA precursors of different molecular weights indicated that the postpolymerization modification reaction proceeds with good to excellent conversion for a diverse variety of functional amines and is essentially independent of the PPFMA precursor molecular weight. The RAFT end group, which was well preserved throughout the polymerization, is cleaved during postpolymerization modification to generate a thiol end group that provides possibilities for further orthogonal chain‐end modification reactions. The degree of postpolymerization modification can be controlled by varying the relative amount of primary amine that is used and random polymethacrylamide copolymers can be prepared via a one‐pot/two‐step sequential addition procedure. Cytotoxicity experiments revealed that the postpolymerization modification strategy does not lead to any additional toxicity compared with the corresponding polymer obtained via direct polymerization, which makes this approach also of interest for the synthesis of biologically active polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4332–4345, 2009     

X‐ray photoelectron and carbon Kα emission measurements and calculations of O‐, CO‐, N‐, and S‐containing substances

X‐ray fluorescence measurements for O‐containing [polyethylene oxide, polyvinyl alcohol, polyvinyl methyl ether], CO‐containing [polyvinyl methyl ketone, polyethylene terephthalate], N‐containing [poly‐4‐vinylpyridine (P4VP), polyaniline oligomer (PAO)], and S‐containing [polyphenylene sulfide] substances are presented. Carbon Kα X‐ray emission spectra (XES) and X‐ray photoelectron spectra (XPS) are compared with our DFT calculations performed with the Amsterdam density functional (ADF) program. The combined analysis of valence XPS and carbon Kα XES allows us to determine the individual contributions from pσ‐ and pπ‐bonding molecular orbitals of the polymers. The ΔSCF calculations yield the accurate C1s core‐electron binding energies (CEBEs) for all carbon sites of the organic compound. We calculate all CEBEs of the model molecules using the ΔE _KS approach. Our simulated C1s photoelectron and C Kα emission spectra are in good agreement with our measurements. We also obtain WD (work function and the other energies) values for the polymers and PAO from the difference between calculated (gas‐phase) and measured (solid) CEBE values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 162–172, 2007     

Using multimodal blends to elucidate the mechanism of flow‐induced crystallization in polymers

The effect of polydispersity on the formation of flow‐induced, oriented morphology in polyolefins is investigated by polarized light imaging and small angle X‐ray scattering. A torsional shear flow was applied at different temperatures to model polyethylene blends (bimodal and trimodal hydrogenated polybutadienes) comprising of two kinds of long chains with different molecular weight (1080 and 1770 kDa) in a matrix of short chains (18 KDa), and the results were compared to those of polydisperse materials. While a single boundary associated with the threshold flow conditions for the onset of oriented morphology is observed in the bimodal blends, two boundaries corresponding to the orientation of the longest chains (1770 kDa) and next longest chains (1080 kDa) are detected in the trimodal blends. The results obtained, herein, are extended by inference to polydisperse polymers. It is demonstrated that the shear rate dependence of the critical specific work parameter for the onset of oriented morphology in polydisperse polymers is dictated by the molecular weight distribution and that the longest chains mainly control the process with some contribution from shorter chains involved in the formation of flow‐induced precursors at higher flow rates. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Pinecone‐like Cu(II) crystal growth on the surface of amine‐group‐immobilized polymers

Field‐emission scanning electron microscopy (FESEM) was used to monitor pinecone‐like Cu(II) crystal growth on polymeric fibers for various growth times. In FESEM images, Cu(II) complexes and Cu(OH)₂ crystal growth on poly(acryloamidino ethylene amine) and poly(acryloamidino diethylenediamine) were observed. Up to an elapsed time of 16 min, crystal growth was observed in only one direction. However, after an elapsed time of 20 h, pinecone‐like crystals covered the entire surfaces of the synthesized polymers. Fourier transform infrared spectroscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy were used for analysis. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1238–1247, 2005     

Synthesis and characterization of PEE‐PEO diblock copolymers with complementary end‐groups for hydrogen‐bond heteroassociation

Poly(ethylethylene‐b‐ethylene oxide) (PEE‐PEO) diblock copolymers with pyridine‐benzoic acid end‐groups for heterodimeric hydrogen bonding were designed as a possible means to noncentrosymmetric organizations by spontaneous self‐assembly. These end‐functionalized polymers were synthesized by anionic living polymerization with protected initiator and terminating reagents. A series of polymeric intermediates with different end‐groups was characterized by proton nuclear magnetic resonance, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and gel permeation chromatography. Preliminary studies of solid‐state organization by differential scanning calorimetry and small‐angle X‐ray scattering provided evidence for a long‐range order that was sensitive to chain length, copolymer composition, and end‐group structure. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 207–219, 2000     

Hydrogen‐bonded supramolecular polymers from derivatives of α‐amino‐ε‐caprolactam: A bio‐based material

Hydrogen‐bonded supramolecular polymers were prepared from the derivatives of α‐amino‐ε‐caprolactam (ACL), obtained from a renewable resource. Several self‐complimentary bis‐ or tetra‐caprolactam monomers were synthesized by varying the number of carbons of the spacer between the hydrogen‐bonding end groups. Physical properties of these hydrogen‐bonded polymers were clearly demonstrated by differential scanning colorimetry, solid‐state NMR, and X‐ray powder diffraction analyses. The supramolecular behavior was also supported by fiber formation from the melt for several of these compounds, and stable glassy materials were prepared from the physical mixtures of two different biscaprolactams. The self‐association ability of ACL was also used by incorporating ACL at the chain ends of low‐molecular weight Jeffamine (M_n = 900 g/mol) using urea and amide linkages. The transformation of this liquid oligomer at room temperature into a self‐standing, transparent film clearly showed the improvement in mechanical properties obtained by the introduction of terminal hydrogen‐bonding groups. Finally, the use of monomers with a functionality of four gave rise to network formation either alone or combination with bifunctional monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of novel liquid‐crystalline copolymers containing thermally stable photochromic groups

To overcome the defects of the thermal instability of azobenzene, a series of novel photochromic, chiral, liquid‐crystalline monomers and polymers were synthesized from (+)‐camphor. The copolymerization of the photochromic monomers with comonomers was carried out. The synthesized monomers and polymers were identified with nuclear magnetic resonance, Fourier transform infrared, and elemental analysis. The composition of the copolymers was estimated with elemental analysis. The specific rotation of the chiral compounds and polymers was evaluated. The thermal stability and phases of the polymers during heating and cooling cycles were studied with differential scanning calorimetry and thermogravimetric analysis. The phases of the polymers were identified with polarized optical microscopy textures and X‐ray diffraction analysis. The distance between the layers of smectic liquid crystals was estimated from the diffraction angles. Photoisomerization of the configurational E/Z structures was investigated with an ultraviolet–visible spectrophotometer with 300‐nm ultraviolet irradiation. The thermal stability of the Z‐structural segment in the polymers was confirmed through the heating of the polymer at 70 °C for over 10 h. The photoisomerization and thermal stability of the C?C bond in the polymeric materials were demonstrated through a series of novel chiral polymers synthesized in this investigation. Both the polarity of the center part and the molecular length at the ends of the molecules were found to be necessary factors for the formation of liquid‐crystalline molecules. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2026–2037, 2007     

Synthesis,solid‐state,and charge‐transport properties of conjugated polythiophene‐S,S‐dioxides

An alkylated semiconducting polymer comprising alternating bithiophene‐[all]‐S,S‐dioxide and aromatic monothiophene units in the polymer backbone was synthesized with the intent of modifying the energy gap and lowest unoccupied molecular orbital for use as a stable n‐type semiconductor. Films spun from this semiconducting polymer were characterized utilizing X‐ray scattering, near edge X‐ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy, and thin‐film field effect transistors to determine how oxidation of the thiophene ring systems impacts the structural and electronic properties of the polymer. The thiophene‐S,S‐dioxide polymers have lower optical and electrical band gaps than corresponding thiophene polymers. X‐ray scattering results indicate that the polymers are well ordered with the π–π stacking distances increased by 0.4 Å relative to analogous thiophene polymers. The electrical stability of these polymers is poor in transistors with a drop in the field effect mobility by approximately one order of magnitude upon addition of just 5% of the thiophene‐S,S‐dioxide unit in a copolymer with thiophene. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Radiation damage in polymer films from grazing‐incidence X‐ray scattering measurements

Grazing‐incidence X‐ray scattering (GIXS) is widely used to analyze the crystallinity and nanoscale structure in thin polymer films. However, ionizing radiation will generate free radicals that initiate crosslinking and/or chain scission, and structural damage will impact the ordering kinetics, thermodynamics, and crystallinity in many polymers. We report a simple methodology to screen for beam damage that is based on lithographic principles: films are exposed to patterns of X‐ray radiation, and changes in polymer structure are revealed by immersing the film in a solvent that dissolves the shortest chains. The experiments are implemented with high throughput using the standard beam line instrumentation and a typical GIXS configuration. The extent of damage (at a fixed radiation dose) depends on a range of intrinsic material properties and experimental variables, including the polymer chemistry and molecular weight, exposure environment, film thickness, and angle of incidence. The solubility switch for common polymers is detected within 10–60 s at ambient temperature, and we verified that this first indication of damage corresponds with the onset of network formation in glassy polystyrene and a loss of crystallinity in polyalkylthiophenes. Therefore, grazing‐incidence X‐ray “patterning” offers an efficient approach to determine the appropriate data acquisition times for any GIXS experiment. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1074–1086     

New π‐conjugated polyaryleneethynylenes containing a 1,3,5‐triazine unit in the main chain: Synthesis and optical and electrochemical properties

A series of new π‐conjugated poly(aryleneethynylene)s containing a 1,3,5‐triazine unit in the main chain were synthesized in yields higher than 70% by polycondensation between dibromophenyl‐1,3,5‐triazine monomers and alkyl‐substituted diethynylbenzene (or diethynylfluorene) comonomers with Pd(PPh₃)₄ and CuI as catalysts in the presence of triethylamine. The polymers had a number‐average molecular weight in the range of 5000–10,000 and showed good solubility in common organic solvents. The polymers were photoluminescent both in solutions and in the solid state. X‐ray diffraction patterns of the powders of the polymers revealed that the polymers were semicrystalline. Electrochemically, the polymers appeared to be reversible under reduction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3797–3806, 2006     

Synthesis and characterization of novel aryl‐ethynylene polymers of tuned rigidity/flexibility

New poly(aryl‐ethynylene) polymers of tuned rigidity/flexibility were synthesized by a palladium‐catalyzed polycondensation. The Sonogashira–Hagihara‐type coupling reaction of 2,5‐diethynyl‐4‐dodecyltoluene with 2,5‐ and/or 3,5‐dibromopyridine led to polymers of different rigidity/flexibility simply by varying the ratio of 2,5‐ to 3,5‐dibromopyridine charged in the polycondensation reaction. The ratio of para–meta linkages at the pyridine moiety in the polymer backbone was determined by NMR spectroscopy. The combination of molecular weight data obtained from vapor pressure osmometry and the use of oligomeric model compounds allowed us to establish a polymer‐specific gel permeation chromatography calibration. Information about the molecular conformation of the polymers in solution were obtained by small‐angle X‐ray scattering (SAXS) experiments. The glass‐transition and melting temperatures varied systematically with the degree of rigidity/flexibility and could be directly related to the conformational changes as reflected from the SAXS data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1919–1933, 2004     

Optimized peptide functionalization of thiol‐acrylate emulsion‐templated porous polymers leads to expansion of human pluripotent stem cells in 3D culture

Highly porous polymers produced by polymerization of the continuous phase of a high internal phase emulsion have been developed as scaffolds for 3D culture of human pluripotent stem cells. These emulsion‐templated polymerized high internal phase emulsion (polyHIPE) materials have an interconnected network of pores that provide support for the cells, while also allowing both cell ingress and nutrient diffusion. Thiol‐acrylate polyHIPE materials were prepared by photopolymerization, which, due to a competing acrylate homopolymerization process, leads to a material with residual surface thiols. These thiols were then used as a handle to allow postpolymerization functionalization with both maleimide and a maleimide‐derivatized cyclo‐RGDfK peptide, via Michael addition under benign conditions. Functionalization was evaluated using an Ellman's colorimetric assay, to monitor the residual thiol concentration, and X‐ray photoelectron spectroscopy. Maleimide was used as a model molecule to optimize conditions prior to peptide‐functionalization. The use of triethylamine as a catalyst and a mixed ethanol‐aqueous solvent system led to optimized reaction between surface‐bound thiols and maleimide. Peptide‐functionalized materials showed improved attachment and infiltration of human pluripotent stem cells over 7 days, demonstrating their promise as a scaffold for 3D stem cell culture and expansion. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1974–1981     

New biodegradable polymers from renewable sources: Polyester‐carbonates based on 1,3‐propylene‐co‐1,4‐cyclohexanedimethylene succinate

α,ω‐Dihydroxy‐terminated copolymeric oligomers of a 1,3‐propylene/1,4‐cyclohexanedimethylene succinate structure were obtained by the thermal polycondensation of 1,3‐propanediol/1,4‐cyclohexanedimethanol/succinic acid mixtures. They were subsequently chain‐extended via phosgene synthesis to high molecular weight aliphatic/alicyclic copolyester‐carbonates. These new polymers, besides having a biodegradable backbone, originate from two monomers, namely, 1,3‐propanediol and succinic acid, which can be obtained by renewable sources. Therefore, they have a potential as environmentally friendly materials. All synthesized materials were characterized in reference to their molecular structure by ¹H NMR and ¹³C NMR. Their molecular weights and molecular weight distributions were determined by size exclusion chromatography, and their main thermal properties were measured by DSC. Spectroscopic characterizations were in full agreement with the proposed structures. 1,4‐Cyclohexanedimethanol was used as a diol comonomer to improve the overall thermal properties of poly(1,3‐propylene succinate). The results of the characterization performed show that the initial expectations were only partially satisfied. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2508–2519, 2001     

Blends of nylon‐6 with phenol‐containing polymers

The miscibility of nylon‐6 with poly(4‐vinylphenol) (PVPh) or poly(1‐hydroxy‐2,6‐methylphenylene) (p‐Cl‐novolac) was studied with differential scanning calorimetry and small‐angle X‐ray scattering techniques. Both PVPh and p‐Cl‐novolac are miscible with nylon‐6 at the molecular level. The presence of the phenolic polymers affects the crystallization of nylon‐6 and suppresses its melting point. PVPh increases the long space order in crystalline nylon‐6 because it increases the thickness of the amorphous layers. In contrast, a small quantity of p‐Cl‐novolac tends to decrease the long space order. It seems that p‐Cl‐novolac distributed in the amorphous regions introduces more order in these regions and makes the amorphous layers thinner. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 841–850, 2001     

Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. II. Influence of side‐chain structure

Solution‐crystallization is studied for two polyfluorene polymers possessing different side‐chain structures. Thermal analysis and temperature‐dependent optical spectroscopy are used to clarify the nature of the crystallization process, while X‐ray diffraction and scanning electron microscopy reveal important differences in the resulting microstructures. It is shown that the planar‐zigzag chain conformation termed the β‐phase, which is observed for certain linear‐side‐chain polyfluorenes, is necessary for the formation of so‐called polymer‐solvent compounds for these polymers. Introduction of alternating fluorene repeat units with branched side‐chains prevents formation of the β‐phase conformation and results in non‐solvated, i.e. melt‐crystallization‐type, polymer crystals. Unlike non‐solvated polymer crystals, for which the chain conformation is stabilized by its incorporation into a crystalline lattice, the β‐phase conformation is stabilized by complexation with solvent molecules and, therefore, its formation does not require specific inter‐chain interactions. The presented results clarify the fundamental differences between the β‐phase and other conformational/crystalline forms of polyfluorenes. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1492–1506