Soluble conjugated polymeric nanoparticles were synthesized through Sonogashira polycondensation between different combinations of multifunctional alkynes and aryl halides in structurally well-defined mesoporous reactors. The growth of the polymeric nanoparticles was controlled by the spatial confinement of the nanoreactors, giving conjugated polymeric nanoparticles with narrow size distribution centered at 5 nm. All the obtained polymers are freely soluble in common solvents and can be fabricated into thin film. Both of the solution and thin film prepared from these polymeric nanoparticles were highly fluorescent, endowing them potential applications in light emitting and other optoelectronic fields. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2285–2290

Novel contrast agents were developed through assembling of Gd^III-containing metallosurfactant (MS) with biocompatible polyelectrolytes sodium hyaluronate (HA), heparinsodium (HS) and dextran sulfate sodium (DSS). The formed polyelectrolyte–surfactant complexes showed different structural patterns as the charge ratio increased, including spherical aggregates, rod-like aggregates and network patterns in monovalent HA system, while spherical structures emerged in multivalent HS and DSS systems. Energy dispersive spectroscopy analysis and scanning electron microscopy mapping showed the presence of Gd^III in these complexes. Inductively coupled plasma atomic emission spectrometry was further used to quantify the contents of Gd^III in the assemblies. T1 magnetic resonance imaging showed that these Gd^III-loaded complexes exhibited relaxivity of up to 63.81 mM⁻¹ s⁻¹, much higher than that of Ominiscan (4.64 mM⁻¹ s⁻¹). The cytotoxicity test in vitro demonstrated the excellent biocompatibility of these complexes, which is essential for clinical application.

Soluble conjugated polymeric nanoparticles are synthesized by Suzuki-type polycondensation of two monomers (A_x + B_y, x>2, y≥2) in the channel of ordered mesoporous silica-supported carbon nanomembranes (nanoreactors). These synthesized soluble conjugated microporous polymers (SCMPs) exhibit uniform particle-size distributions and well-controlled particle sizes. The control of particle size stems from the fact that the polycondensations exclusively take place inside the mesochannels of the nanoreactors. Photoluminescence studies show that polymeric nanoparticles with tetraphenylethene and pyrene substructures are highly fluorescent. The combination of both physical stability and processability offered by the soluble polymeric nanoparticles makes them particularly attractive in light emitting and other optoelectronic applications.

Catalytic reactions occurring on oxide-supported Cu and Cu-supported oxide catalysts are of fundamental interest in both industrial and scientific fields. Though the interface between Cu and oxide species has been regarded as the reaction site, the exact role of the interface in the catalytic reactions is not fully understood yet. In this work, by using a model system including CuO chains supported on Cu(1 1 0) and an organic molecule with alkynyl and aldehyde groups, we attempted to obtain a fundamental understanding of the role of the interface in the catalytic reactions. A combination of high-resolution scanning tunneling microscopy imaging and density functional theory calculations provided direct evidence at the atomic scale that the interface between the CuO chains and the Cu(1 1 0) surface is the most favorable site for the adsorption and activation of organic molecules, and the oxygen of CuO has an activity to oxidize both the alkynyl and aldehyde groups of the molecules adsorbed at the interface.

Hydrophilic polymeric nanoparticles are synthesized through a Bergman cyclization- mediated intramolecular chain collapse of structurally well-defined linear polymers, and then used as size-tunable nanoreactors to fabricate and encapsulate quantum dots in a one-pot reaction. Crystalline quantum dots are formed in all of these nanoreactors and visualized by transmission electron microscopy. Smaller nanoreactors produce one quantum dot each while larger nanoreactors form a number, resulting in fluorescence quenching. By controlling the molecular weight of the linear polymer precursor, a variable number of nanocrystals are fabricated and assembled in a single nanoreactor.

A method for covalent functionalization of multiwalled carbon nanotubes (MWCNTs) was developed using the free radicals generated through Bergman cyclization of enediyne-containing compounds. Four enediyne-bearing Frechet type dendrimers were synthesized in good quantities and characterized. Then, the enediyne-containing molecules were reacted with MWCNTs in N-methyl-2-pyrrolidinone at 206 °C under nitrogen. The structure and morphology of the resulting products were characterized by thermogravimetric analysis, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy. The dendrimer-functionalized MWCNTs showed good solubility/dispersibility in common organic solvents and polymer solutions. They were used in the formation of polymer composites through electrospinning with polycaprolactone. The results confirmed the surface functionalization of MWCNTs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Employing enediynes as crosslinking precursors, a novel yet efficient strategy, namely photo-triggered Bergman cyclization, was integrated with intramolecular chain collapse to yield polymeric nanoparticles with the size regime below 20 nm. Enediyne motif was designed delicately to possess a high photo-reactivity, with the double bond locked in a methyl benzoate ring while triple bonds substituted with phenyls. Single electron transfer-living radical polymerization was conducted to provide linear acrylate copolymers with controlled molecular weights and narrow polydispersities. Poly(butylarylate-co-5) went through UV-irradiation with a concurrent Bergman cyclization, resulting in well-defined ultrafine polymeric nanoparticles. Results from NMR, Raman scattering, photoluminescence and UV-vis spectra corroborated the presence of conjugative structures in the polymeric nanoparticles, indicating the occurrence of photo-induced Bergman cyclization. A series of other acrylate-based nanoparticles were investigated to confirm the applicability of such a unique strategy in thermal sensitive but UV-stable polymeric structures, making photo-Bergman cyclization a promising tool towards polymeric nanoparticles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

In this article, dendronized polymers with rigid backbones were synthesized from enediyne-containing Frechet-type dendrimers. Two generations of dendrimers were conically incorporated with 3-(2-(2-(trimethylsilyl)ethynyl)phenyl)prop-2-yn-1-ol. The trimethylsilyl protection groups of enediyne units were subsequently removed, and two types of brush polymers with rigid conjugated backbone were prepared through Bergman cyclization polymerization at elevated temperature under vacuum. The dendronized polymers were characterized with GPC, IR, UV–vis, and NMR spectroscopy. Furthermore, the morphology of the dendronized polymer was revealed by atomic force microscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

A series of enediyne containing chiral phthalimides were synthesized through Sonogashira coupling reactions. These enediynes were then subjected to thermal Bergman cyclization under vacuum. Polynaphthalenes with pendant chiral groups were obtained and characterized using GPC, IR spectroscopy, NMR spectroscopy, UV–Vis spectroscopy, and photoluminescence analysis. Under properly optimized conditions, the chirality of chiral directing group was maintained according to CD spectra of final products. After removal of chiral directing groups, weak CD signals representative of main chain chirality were visible. Further modification of the structure of the enediyne compounds will facilitate the synthesis of chiral polynaphthalene through this rather simple way. Extension of the Bergman cyclization to polymer chemistry is promising in the construction of novel polymers with rigid polyarene backbones. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2187–2193, 2010

In this work, pristine multiwalled carbon nanotubes (MWNTs) were functionalized by utilizing the free radicals generated through Bergman cyclization of enediyne containing compounds 3. Polyesters were subsequently grafted from the surface of MWNTs through ring-opening polymerization of ε-caprolactone or lactide initiated by free hydroxy groups generated after hydrolysis of ester groups. Functionalized MWNTs were characterized with a variety of techniques, including TGA, NMR, IR, UV–vis, TEM, and Raman spectroscopy. After surface modification, MWNTs showed good solubility in common organic solvents and polymer solutions. Fabrication of MWNTs polymer nanocomposites was revealed through electrospinning with polycaprolactone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010