Homopolycyclotrimerization of A4‐type tetrayne: A new approach for the creation of a soluble hyperbranched poly(tetraphenylethene) with multifunctionalities

A tetraphenylethene‐containing A₄‐type tetrayne, named 1,1,2,2‐tetrakis(4‐ethynylphenyl)ethene is synthesized and its TaCl₅‐Ph₄Sn catalyzed homopolycyclotrimerization affords hyperbranched poly(tetraphenylethene) with high molecular weight (M_w = 280,000) in high yield (97%). The polymer shows good solubility and high thermal stability. It is aggregation‐enhanced emission (AEE)‐active and functions as a fluorescent chemosensor for explosive detection with a superamplification effect and large quenching constants up to 758,000 M^?1. The polymer shows high and tunable refractive indices (RI = 1.9288?1.6746) in a wide wavelength region. Porous fluorescent polymer thin film is prepared by breath figure (BF) methods and real‐time monitoring of the elusive BF formation process is realized. Photolithography of the thin films readily generates well‐resolved fluorescent photopattern without and with porous secondary structure. The polymer is metallified and pyrolysed to give magnetic ceramics with high magnetic susceptibilities (M_s = 83 emu/g) and near‐zero coercivity (H_c = 0.08 kOe). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4752–4764     

Conjugated polymer nanoparticles with aggregation induced emission characteristics for intracellular Fe3+ sensing

In this article, a novel zwitterionic conjugated polyelectrolyte containing tetraphenylethene unit was synthesized via Pd‐catalyzed Sonogashira reaction. The resulting polymer (P2), which exhibited typical aggregation‐induced emission (AIE) properties, was weakly fluorescent in dilute DMSO solution and showed bright fluorescence emissions when aggregated in DMSO/water mixtures or fabricated into conjugated polymer nanoparticles (CPNs). The nanoparticles from P2 could be prepared by reprecipitation method with an average diameter around 23 nm. Notably, the cell‐staining efficiencies of lipid‐P2 nanoparticles could be enhanced with lipid encapsulation and these nanoparticles were endocytosed via caveolae‐mediated and clathrin‐mediated endocytosis pathways. Furthermore, the lipid‐P2 nanoparticles with low cytotoxicity, high photostability and efficient cell staining ability could be employed for in vitro detection of Fe³⁺ ions in A549 cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1686–1693     

Design and property of thermoresponsive core–shell fluorescent nanoparticles via RAFT polymerization and suzuki coupling reaction

The polymerization of a 2,7‐dibromocarbazole‐containing functional monomer, 6‐(2,7‐dibromo‐9H‐carbazol‐9‐yl)hexyl methacrylate (DBCzMA), was successfully carried out via the reversible addition‐fragmentation chain transfer (RAFT) technology. The polymerization behavior possessed the feature of “living”/controlled radical polymerization, for example, the first‐order kinetics, the linear increase of the molecular weight of the polymer with the monomer conversion and relatively narrow molecular weight distribution (M_w/M_n ≤ 1.27). The amphiphilic copolymers, poly(DBCzMA_m‐b‐NIPAM_n), with different chain length of poly(DBCzMA) and poly(N‐isopropylacrylamide) (PNIPAM), were successfully prepared via RAFT chain‐extension reaction, using poly(DBCzMA) as the macromolecular chain transfer agent (macro‐CTA) and NIPAM as the second monomer. Modification of 2,7‐dibromide groups in amphiphilic copolymer poly(DBCzMA‐b‐NIPAM) via Suzuki coupling reaction employed 2,7‐bis(4′,4′,5′,5′‐tetramethyl‐1′,3′,2′‐dioxaborolan‐2′‐yl)‐N?9″‐heptadecanylcarbazole as the other reaction material to afford a poly(2,7‐carbazole)‐containing crosslinked materials. The stable and uniform core–shell fluorescent nanoparticles were successfully prepared in water. The formed fluorescent nanoparticles showed good thermoresponsive properties, which is confirmed by dynamic light scattering observation. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4021–4030     

Influence of monomer type on miniemulsion polymerization systems stabilized by graphene oxide as sole surfactant

Based on a recent report [J. Polym. Sci. Part A. Polym. Chem. 2013 , 51, 47–58] whereby we demonstrated the synthesis of polystyrene nanoparticles by miniemulsion polymerization stabilized by graphene oxide (GO) nanosheets as sole surfactant, we hereby report the synthesis of hybrid polymer nanoparticles of several members of the (meth)acrylate family as well as the cross‐linker divinylbenzene via the same approach. The nature of the resultant emulsion is strongly linked to the polarity of the monomer used; monomers with a relatively small polar component (based on Hansen solubility parameters) such as lauryl methacrylate and benzyl methacrylate, in addition to styrene, generate stable emulsions that can be effectively polymerized. Particularly polar monomers (e.g., methyl acrylate and methyl methacrylate) formed kinetically stable emulsions in the presence of GO, however rapid coagulation occurred during polymerization. Electron microscopy analysis reveals the formation of polymer nanoparticles with size distribution between 200 and 1000 nm with roughened surface morphologies, indicative of GO sheets adsorbed at the interface. The results of this work demonstrate the applicability of this synthetic route for specific monomers in the preparation of novel graphene‐based polymeric materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5153–5162     

A helical chiral polymer‐based chromo‐fluorescence and CD response sensor for selective detection of trivalent cations

A novel chiral (S)‐BINAM‐based fluorescent polymer sensor was designed and synthesized by the polymerization of 4,4′‐((2,5‐dibutoxy‐1,4‐phenylene)bis(ethyne‐2,1‐diyl))‐dibenzaldehyde ( M‐1 ) with (S)‐2,2′‐binaphthyldiamine (S‐BINAM, M‐2 ) via Schiff's base formation. The resulting helical chiral polymer sensor exhibited remarkable “turn‐on” bright blue fluorescence color upon the addition of trivalent metal ions under a commercially available UV lamp; this change can be clearly observed by the naked eye for direct visual discrimination at low concentration. More importantly, the addition of trivalent metal cations can lead to a most pronounced change of CD spectra of the chiral polymer indicating this kind chiral sensor can also be used as a sole probe for selective recognition of trivalent metal cations based on CD spectra. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4070–4075     

Prepolymerization and postpolymerization functionalization approaches to fluorescent conjugated carbazole‐based glycopolymers via “click chemistry”

Facile prepolymerization and postpolymerization functionalization approaches to prepare well‐defined fluorescent conjugated glycopolymers through Cu(I)‐catalyzed azide/alkyne “Click” ligation were explored. Two well‐defined carbazole‐based fluorescent conjugated glycopolymers were readily synthesized based on these strategies and characterized by ¹H NMR, ¹³C NMR, IR spectra, and UV‐vis spectra. The “Click” ligation offers a very effective conjugation method to covalently attach carbohydrate residues to fluorescent conjugated polymers. In addition, the studies of carbohydrate–lectin interactions were performed by titration of concanavalin A (Con A) to D ‐glucose‐bearing poly(anthracene‐alt‐carbazole) copolymer P‐2 resulting in significant fluorescence quenching of the polymer due to carbohydrate–lectin interactions. When peanut agglutinin (PNA) was added, no distinct change in the fluorescent properties of P‐2 was observed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2948–2957, 2009     

Fabrication of a nanohybrid of conjugated polymer nanoparticles and graphene oxide for biosensing of trypsin

Conjugated polymers containing triphenylamine group are synthesized via Suzuki coupling polymerization. Fluorescent‐conjugated polymer nanoparticles (CPN) are prepared by reprecipitation method using the newly synthesized conjugated polymer. CPN can be encapsulated with polyarginine by electrostatic interaction. The CPN modified with polyarginine exhibit excellent interaction with graphene oxide (GO) which is chemically modified with hydrophilic groups that possesses negative charge, which, in turn, induces the quenching of the fluorescence of CPN upon formation of CPN–GO nanohybrid. Upon exposure to trypsin, the quenched fluorescence is recovered by release of CPN from the nanohybrid, because trypsin cleaves the polyarginine linkage, resulting in weakening of interaction between CPN and GO. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1898–1904     

Anisotropic janus magnetic polymeric nanoparticles prepared via miniemulsion polymerization

Anisotropic Janus magnetic polymeric nanoparticles are prepared via the miniemulsion polymerization of styrene and acrylic acid monomers in the presence of oleic acid‐coated magnetic nanoparticles (MNPs). The controllable phase separation between the polymer matrix and the encapsulated MNPs is a key success factor to produce Janus morphology. The effects of MNPs, 2,2′‐azobis(2‐isobutyronitrile) and sodium dodecyl sulfate contents, on the morphology, chemical composition and colloidal stability of the prepared Janus hybrid particles are investigated. Besides the determination of polymerization conversion, zeta potential, size analysis, TGA, and TEM are applied for characterization of the anisotropic particles. The results show the stable spherical Janus particles containing MNPs (15 wt % magnetic content) located on one side of each polymer particle. The anisotropic submicron Janus magnetic polymeric particles (250 nm) can be easily separated by an external magnet. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4779–4785     

Fluorescent PMMA/MEH‐PPV electrospun nanofibers: Investigation of morphology,solvent, and surfactant effect

Electrospinning is a powerful technique to produce nanofibers of tunable diameter and morphology for medicine and biotechnological applications. By doping electrospun nanofibers with inorganic and organic compounds, new functionalities can be provided for technological applications. Herein, we report a study on the morphology and optical properties of electrospun nanofibers based on the conjugated polymer poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH‐PPV) and poly(methylmethacrylate) (PMMA). Initially, we investigate the influence of the solvent, surfactant, and the polymer concentration on electrospinning of PMMA. After determining the best conditions, 0.1% MEH‐PPV was added to obtain fluorescent nanofibers. The optical characterizations display the successful impregnation of MEH‐PPV into the PMMA fibers without phase separation and the preservation of fluorescent property after fiber electrospinning. The obtained results show the ability of the electrospinning approach to obtain fluorescent PMMA/MEH‐PPV nanofibers with potential for optical devices applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1388–1394     

End‐group functionalization and postpolymerization modification of helical poly(isocyanide)s

This contribution presents the synthesis of helical alkyne‐terminated polymers using a functionalized Nickel complex to initiate the polymerization of menthylphenyl isocyanides. The resulting polymers display low dispersities and controlled molecular weights. Copper‐catalyzed azide/alkyne cycloadditions (CuAAC) are performed to attach various azide‐containing compounds to the polymer termini. After azido‐phosphonate moiety attachment the polymer displays a signal at 25.4 ppm in the ³¹P NMR spectrum demonstrating successful end‐group functionalization. End‐group functionalization of a fluorescent dye allows to determine the functionalization yield as 89% (±8). Successful ligation of an azide‐functionalized peptide sequence (M_KLA = 1547 g/mol) increases the M_n from 5100 for the parent polymer to 6700 for the bioconjugate as visualized by GPC chromatography. Analysis by CD spectroscopy confirms that the helical conformation of the poly(isocyanide) block in the peptide–polymer conjugate is maintained after postpolymerization modification. These results demonstrate an easy, generalizable, and versatile strategy toward mono‐telechelic helical polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2766–2773     

Functional polysilanes of relevance for the synthesis of Au and Au–Pd nanoparticle assemblies—a study on the role of polymer‐supported thioether side chains

Linear polysilanes, [{PhHSi}_x{Ph(RSCH₂CH₂CH₂)Si}_1?x]_n [R = n‐dodecyl ( 1 ), n‐hexyl ( 2 ), n‐butyl ( 3 )], have been synthesized and their reactivity with HAuCl₄·3H₂O (Polymer:Au = 10:1, RT, toluene) examined to gain an insight into the role of polymer‐supported thioether groups in the stabilization of in situ generated gold nanoparticles (AuNPs). The method allows a simple approach for expeditious synthesis of assemblies of AuNPs comprising of well‐separated individual nanoparticles of average diameter 4.5 ± 1.9 nm. In this regard, polysilane 1 with dodecyl side chains serves as a superior matrix than 2 and 3 and confers long shelf‐life stability to the nanoparticle assembly. The structural attributes are preserved in Au–Pd bimetallic nanoparticles which have been synthesized from the polymer‐gold nanoassembly. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities

Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710     

Design and synthesis of fluorescent core–shell nanoparticles with tunable lower critical solution temperature behavior and metal‐enhanced fluorescence

In this article, the preparation of fluorescent nanohybrids with core–shell structure and metal‐enhanced fluorescence (MEF) effect was presented. The fluorescent core–shell nanohybrids were prepared using silver nanoparticles (AgNPs) as cores and fluorophore tethered thermoresponsive copolymers with tunable lower critical solution temperature (LCST) from 15 to 90 °C as shells. These thermoresponsive copolymers were synthesized by the random copolymerization of oligo(ethylene oxide) acrylate and di(ethylene oxide) ethyl ether acrylate using reversible addition–fragmentation chain transfer polymerization and grafted on to AgNPs surface via Ag–S coordination interaction. By thermal manipulation of polymer spacer between AgNPs and fluorophores, the tunable MEF was achieved. It was also revealed that the fluorescent nanohybrids would exhibit maximal MEF when the polymerization degree was tuned to 350. The manipulation of the solution temperatures below and above LCST resulted in switchable MEF behavior. In addition, the phase transition process of the thermoresponsive copolymer was also studied by MEF effect using this fluorescent core–shell nanohybrid design. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 87–95     

Electrochemical fluorescence switching properties of conjugated polymers composed of triphenylamine,fluorene, and cyclic urea moieties

The study of the electrochemical fluorescence switching properties of the conjugated copolymers containing fluorene, triphenylamine, and 1,3‐diphenylimidazolidin‐2‐one moieties is reported. The polymers show high fluorescence quantum yields, excellent thermal stability, and good solubility in polar organic solvents. While the polymer emits blue light under UV irradiation, the fluorescence intensity is quenched upon electrochemical oxidation. The fluorescent behavior can be reversibly switched between nonfluorescent (oxidized) state and strong fluorescence (neutral) state with a high contrast ratio (I_f/I_f0) of 16.3. The role of the electrochemical oxidation of the triphenylamine moieties is to generate the corresponding radical cations that lead to fluorescence quenching in the solid matrix. © 2012 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym Chem, 2012     

A novel polymer gel electrolyte: Direct polymerization of ionic liquid from surface of silica nanoparticles

A novel polymer electrolyte is synthesized by directly grafting poly ionic liquids onto silica nanoparticles. The kinetic study of this surface‐initiated polymerization has also been included. A gel‐state electrolyte is formed by mixing this type of polymer/silica nanocomposite with ionic liquids under 60 °C, which exhibits an excellent conductivity of 0.8 mS/cm at room temperature and 14.7 mS/cm at 90 °C. In addition, the mechanism of gel formation has also been discussed in this article. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 121–127     

From single‐chain folding to polymer nanoparticles via intramolecular quadruple hydrogen‐bonding interaction

Single‐chain folding via intramolecular noncovalent interaction is regarded as a facile mimicry of biomacromolecules. Single‐chain folding and intramolecular crosslinking is also an effective method to prepare polymer nanoparticles. In this study, poly(methyl methacrylate‐co?2‐ureido‐5‐deazapterines functionalized ethylene methacrylate) (P(MMA‐co‐EMA‐DeAP)) is synthesized via free radical polymerization. The single‐chain folding of P(MMA‐co‐EMA‐DeAP) and the formation of the nanoparticles in diluted solution (concentration <0.005 mg/mL) are achieved via supramolecular interaction and intramolecular collapsing during the disruption‐reformation process of the hydrogen bonding triggered by water. The size and the morphology of the nanoparticles are characterized by dynamic light scattering, transmission electron microscope, and atomic force microscope. The results show that the size of the nanoparticles depends on the molecular weight of the polymer and the loading of 2‐ureido‐5‐deazapterines functionalized ethylene methacrylate (EMA‐DeAP) on the polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1832–1840     

A visible light responsive azobenzene‐functionalized polymer: Synthesis,self‐assembly,and photoresponsive properties

A novel visible light responsive random copolymer consisting of hydrophobic azobenzene‐containing acrylate units and hydrophilic acrylic acid units has been prepared. The azobenzene molecule bearing methoxy groups at all four ortho positions is readily synthesized by one‐step conversion of diazotization. The as‐prepared polymer can self‐assemble into nanoparticles in water due to its amphiphilic nature. The tetra‐o‐methoxy‐substituted azobenzene‐functionalized polymer can exhibit the trans‐to‐cis photoswitching under the irradiation with green light of 520 nm and the cis‐to‐trans photoswitching under the irradiation with blue light of 420 nm in both solution and aggregate state. The morphologies of the self‐assembled nanoparticles are revealed by TEM and DLS. The controlled release of loaded molecules from the nanoparticles can be realized by adjusting pH value since the copolymer possesses pH responsive acrylic acid groups. The fluorescence of loaded Nile Red in the nanoparticles can be tuned upon the visible light irradiation. The reversible photoswitching of the azobenzene‐functionalized polymer under visible light may endow the polymer with wide applications without using ultraviolet light at all. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2768–2775     

Preparation of glycopolymer‐substituted gold nanoparticles and their molecular recognition

Glycopolymer‐substituted gold nanoparticles were prepared via living radical polymerization with a reversible addition‐fragmentation chain transfer (RAFT) reagent. Polyacrylamide derivatives with α‐mannose (α‐Man) and N‐acetyl‐β‐glucosamine (β‐GlcNAc) were synthesized and hydrogenated to obtain thiol‐terminated polymer. The thiol‐terminated glycopolymers were mixed with gold nanoparticles to yield the polymer substituted gold nanoparticles with various diameters, which aggregated on addition of saccharide‐recognition proteins (lectins). The aggregation properties were analyzed using transmission electron microscopy and UV spectra. Molecular recognition was studied with E. coli, which induced aggregation of the nanoparticles at the cell periphery. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1412–1421, 2009     

New environmentally responsive fluorescent N‐isopropylacrylamide copolymer and its application to DNA sensing

We report two novel multifunctional copolymers consisting of a temperature‐responsive poly(N‐isopropylacrylamide) (PNIPAA) segment and a fluorescent fluorene‐containing acrylic polymer segment with pH responsiveness and/or DNA‐sensing ability. The functional acrylic monomer with a fluorene dimer side group substituted with amino units was synthesized first. Then, it was copolymerized with N‐isopropylacrylamide to result in a new water‐soluble, fluorescent PNIPAA copolymer ( P1 ). The fluorescent properties of P1 under neutral and acidic conditions did not change with the temperature. However, significant variation was observed under basic conditions. The protonation of the amino moiety at a low pH improved the solubility and prevented aggregation for fluorescence quenching, but not under the basic conditions. Although aggregation of the fluorene units was significant at room temperature under basic conditions, the aggregation was resolved at a temperature above the lower critical solution temperature. These findings indicated the pH‐ and temperature‐responsive characteristics of P1 . Moreover, after the amino groups were quaternized, the obtained polymer could be used as a biosensor because the fluorescence intensity was quenched with the addition of DNA. This study demonstrates that multifunctional materials with pH‐ and temperature‐sensing characteristics and biological molecules could be realized by the incorporation of a functional fluorene‐containing moiety with PNIPAA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5495–5504, 2006     

Engineering of new crosslinked near‐infrared fluorescent polyethylene glycol bisphosphonate nanoparticles for bone targeting

Bisphosphonates (BPs) are nonhydrolysable pyrophosphate analogs with high affinity to hydroxyapatite (HAP, bone mineral) and are mainly used for treatment of various bone diseases. In this study, we designed and prepared crosslinked BP nanoparticles by dispersion copolymerization of three monomers: methacrylate PEG bisphosphonate, N‐(3‐aminopropyl) methacrylamide, and tetra(ethylene glycol) diacrylate. The size and size distribution of these PEG‐BP nanoparticles were controlled by changing various polymerization parameters. These BP particles possess dual functionality: covalent attachment of a dye (e.g., near IR fluorescent dye) or drug to the nanoparticles through the primary amine groups belonging to the aminopropyl methacrylamide monomeric units and chelation to the bone mineral HAP through the BP groups belonging to the methacrylate PEG bisphosphonate monomeric units, for enhanced long term bone‐targeted imaging and therapy applications. Body distribution of the optimal crosslinked BP nanoparticles was tested on a chicken embryo model via intravenous administration. This study indicated that the fluorescence intensity of the all organs (e.g., blood, spleen, liver, kidney, and heart) except the bones decreased significantly within 48 h (p < 0.05) while that of the bones hardly changed over that time (p > 0.05). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4282–4291