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Showing papers by "Wang Zhang Yuan published in 2012"


Journal ArticleDOI
TL;DR: The AIE‐active fluorogen‐loaded BSA NPs show an excellent cancer cell uptake and a prominent tumor‐targeting ability in vivo due to the enhanced permeability and retention effect.
Abstract: Light emission of 2-(2,6-bis((E)-4-(diphenylamino)styryl)-4H-pyran-4-ylidene)malononitrile (TPA-DCM) is weakened by aggregate formation. Attaching tetraphenylethene (TPE) units as terminals to TPA-DCM dramatically changes its emission behavior: the resulting fluorogen, 2-(2,6-bis((E)-4-(phenyl(4′-(1,2,2-triphenylvinyl)-[1,1′-biphenyl]-4-yl)amino)styryl)-4H-pyran-4-ylidene)malononitrile (TPE-TPA-DCM), is more emissive in the aggregate state, showing the novel phenomenon of aggregation-induced emission (AIE). Formulation of TPE-TPA-DCM using bovine serum albumin (BSA) as the polymer matrix yields uniformly sized protein nanoparticles (NPs) with high brightness and low cytotoxicity. Applications of the fluorogen-loaded BSA NPs for in vitro and in vivo far-red/near-infrared (FR/NIR) bioimaging are successfully demonstrated using MCF-7 breast-cancer cells and a murine hepatoma-22 (H22)-tumor-bearing mouse model, respectively. The AIE-active fluorogen-loaded BSA NPs show an excellent cancer cell uptake and a prominent tumor-targeting ability in vivo due to the enhanced permeability and retention effect.

603 citations


Journal ArticleDOI
TL;DR: In this paper, the authors report the triphenylamine (TPA) and 2,3,3-triphenylacrylonitrile (TPAN) based EEM architectures, namely, TPA3TPAN and DTPA4TPAN.
Abstract: Emissive electron donor–acceptor (D–A) conjugates have a wide variety of applications in biophotonics, two-photon absorption materials, organic lasers, long wavelength emitters, and so forth. However, it is still a challenge to synthesize high solid-state efficiency D–A structured emitters due to the notorious aggregation-caused quenching (ACQ) effect. Though some D–A systems are reported to show aggregation-induced emission (AIE) behaviors, most are only selectively AIE-active in highly polar solvents, showing decreased solid-sate emission efficiencies compared to those in nonpolar solvents. Here we report the triphenylamine (TPA) and 2,3,3-triphenylacrylonitrile (TPAN) based D–A architectures, namely, TPA3TPAN and DTPA4TPAN. Decoration of arylamines with TPAN changes their emission behaviors from ACQ to AIE, making resulting TPA3TPAN and DTPA4TPAN nonluminescent in common solvents but highly emissive when aggregated as nanoparticles, solid powders, and thin films owing to their highly twisted configurat...

451 citations


Journal ArticleDOI
TL;DR: By integrating N,N-dimethyl (donor, D) and fumaronitrile (acceptor, A) groups with the biphenyl fluorogen, which has an aggregation-induced emission (AIE) property, Wang et al. as mentioned in this paper obtained the target molecule 2-(4-bromophenyl)-3-(4′-(dimethylamino)-biphenyl-4-yl) fumaritrile, which is a red-to-near-infrared-emitting fluorogen with emission peaks at 653 and 710 nm
Abstract: By integrating N,N-dimethyl (donor, D) and fumaronitrile (acceptor, A) groups with the biphenyl fluorogen, which has an aggregation-induced emission (AIE) property, we have obtained the target molecule 2-(4-bromophenyl)-3-(4′-(dimethylamino)-biphenyl-4-yl) fumaronitrile (BDABFN). BDABFN is a red-to-near-infrared-emitting fluorogen with emission peaks at 653 and 710 nm for its amorphous and crystal solids, respectively. BDABFN shows an evident aggregation-induced emission property, and the fluorescence quantum efficiency of its solid is 26.5%. Cystallographic data indicate that there is no π–π stacking, and neither J- nor H-aggregates are observed between the adjacent molecules. The existence of multiple C–H···π bonds between the adjacent molecules restricts the intramolecular rotation of the D and A moieties and enables the fluorogen to emit intensely in the solid states. Meanwhile, because of strong intramolecular D–A interaction, BDABFN exhibits pronounced solvatochromism, and the fluorescence peak red-...

137 citations


Journal ArticleDOI
TL;DR: In this paper, three dimethyltetraphenylsiloles (DMTPSs) symmetrically substituted on their 2,5-positions with electron-accepting (A), i.e.aldehyde (ALD) and dicyanovinyl (DCV) or donating (D), were designed and synthesized via facile reaction procedures.
Abstract: Three dimethyltetraphenylsiloles (DMTPSs) symmetrically substituted on their 2,5-positions with electron-accepting (A), i.e.aldehyde (ALD) and dicyanovinyl (DCV) or donating (D), i.e.diphenylamine (DPA) moieties were designed and synthesized via facile reaction procedures. The propeller-shaped luminogens exhibit aggregation-induced/enhanced emission characteristics with high quantum yields up to 74.0% in the solid state, and are thermally stable, showing high degradation temperatures and melting points up to 388 and 246 °C, respectively. Thanks to the contained A or D moieties, the siloles show intriguing solvatochromism: DMTPS-ALD exhibits almost no response to solvents due to the balance of electron affinities of the aldehyde and the silole core. Whereas, DMTPS-DCV and DMTPS-DPA possess outward intramolecular charge-transfer (ICT) from the silole core and the phenyl rings on its 3,4-positions to dicyanovinyl groups, and inward ICT from diphenylamine groups to the silole core, respectively, showing positive solvatochromism. A multilayer organic light-emitting diode using DMTPS-DPA among the luminogens as an emitter layer shows the highest performance with turn-on voltage, maximum luminance, current, power, and external efficiencies of 3.1 V, 13405 cd m−2, 8.28 cd A−1, 7.88 lm W−1, and 2.42%, respectively. Furthermore, DMTPS-DPA can also serve in hole-transporting layers because of its high hole-mobility. Therefore, the incorporation of a triphenylamine moiety into a silole system not only changes the classical aggregation-caused quenching fluorophore into AEE-active DMTPS-DPA, another example of “turning stone into gold”, but also enhances the hole-transporting ability of siloles.

111 citations


Journal ArticleDOI
TL;DR: In this paper, a combination of aggregation-induced emission active luminogens and mesogens generates high solid-state efficiency luminescent liquid crystals, thus resolving the problem of aggregationcaused quenching normally occurs in the fabrication of luminecent mesomorphic films.
Abstract: Rational combination of aggregation-induced emission active luminogens and mesogens generates high solid-state efficiency luminescent liquid crystals, thus resolving the problem of aggregation-caused quenching normally occurs in the fabrication of luminescent mesomorphic films.

110 citations


Journal ArticleDOI
TL;DR: In this article, the authors presented a proof-of-concept example for the designation of organic soft porous crystals with a conjugated fluorophore and demonstrated the successful achievement of softness, porosity and crystallization ability.
Abstract: Novel fluorescent organic soft porous crystals have been designed and prepared based on a multi-substituted silole bearing 1-phenyl-2,2-dicyanoethene moieties (molecule 8). 8 exhibited a series of emission colors, ranging from yellow to dark red with an over 70 nm shift of emission maximum. Molecule 8 also showed the ability to reversibly switch between different solid states, and a typical mechanofluorochromism was observed by cyclic operation of the grinding–heating–cooling processes. In addition, two single crystals (O and R) were successfully obtained in proper conditions, and the crystallographic data indicated that crystal O and R had reasonable hollow structures, inside which different solvent molecules were selectively encapsulated. More importantly, we have presented a proof-of-concept example of the strategy for the designation of organic soft porous crystals with a conjugated fluorophore and demonstrated the successful achievement of softness, porosity and crystallization ability. This design strategy is instructive to design and construct organic soft porous crystals with other conjugated building blocks and develop novel smart and stimuli-responsive photo/electronic materials.

63 citations


Journal ArticleDOI
TL;DR: In this paper, a typical dye molecule with aggregation-induced-emission (AIE) characteristics, Tetraphenylethene (TPE), was used for self-assembly of fluorescent functional materials.
Abstract: Self-assembly of fluorescent functional materials has attracted increasing interest in the fabrication of optoelectronic and biological nanodevices. Tetraphenylethene (TPE) is a typical dye molecule with aggregation-induced-emission (AIE) characteristics. Melding TPE carrying triple-bond functionality with diazide-containing biphenyl through “click” chemistry generates AIE-active luminogens [1,1′-biphenyl]-4,4′-diyl bis(6-(4-(4-(1,2,2-triphenylvinyl)phenyl)-1H-1,2,3-triazol-1-yl) hexanoate) [1(5)] and [1,1′-biphenyl]-4,4′-diyl bis(11-(4-(4-(1,2,2-triphenylvinyl)phenyl)-1H-1,2,3-triazol-1-yl) undecanoate) [1(10)] with solid state efficiencies up to unity. Slow addition of dilute THF solutions of 1(m) (m = 5, 10) into nonsolvents such as n-hexane and water yields self-assembled white wooly solids. TEM and SEM observations reveal the (helical) nanofibrous structure of the aggregates. Upon cooling from their concentrated hot solutions, 1(m) readily precipitate. Meanwhile, they can also form gels at high concentrations. Both precipitates and gels of 1(m) exhibit structures similar to those of the aggregates formed in nonsolvents. These results indicate that 1(m) can facilely self-assemble into high emission efficiency (helical) nanofibers, thus paving the way for their optoelectronic and biological applications.

61 citations


Journal ArticleDOI
TL;DR: In this paper, the effects of processing methods (mechanical mixing and ball milling homogenization) on the fracture toughness of as-received and phenylphosphonic acid (PPA) treated halloysite-epoxy composites were investigated.

57 citations


Journal ArticleDOI
TL;DR: All of the polymers possessed good film formability, and UV irradiation of the thin films induced simultaneous photobleaching and cross-linking, thus making them applicable in the fabrication of 2D and 3D patterns.
Abstract: Triphenylamine (TPA)-based conjugated hyperbranched poly(aryleneethynylene)s (PAEs), hb-P1/2, hb-P1/3, and hb-P1/4, were synthesized with high molecular weights and good solubilities through Sonogashira coupling reactions. These PAEs exhibited outstanding thermal stabilities and different emission behaviors. Tetraphenylethene (TPE)-containing hb-P1/2 fluoresced faintly in THF, although its light emission was enhanced by aggregate formation in aqueous media or in thin films, thereby exhibiting an aggregation-induced emission-enhancement (AIEE) effect. Whereas 1,1,2,3,4,5-hexaphenylsilole (HPS)-bearing hb-P1/3 showed no significant change in emission intensity with increasing water content in aqueous media, hb-P1/4, which consisted of TPA-fluorenone donor-acceptor groups, presented almost identical absorptions, but both positive and negative solvatochromic emissions in various solvents. A superquenching effect was observed in the picric-acid-detection process by using nanosuspensions of hb-P1/2. All of the polymers possessed good film formability. UV irradiation of the thin films induced simultaneous photobleaching and cross-linking, thus making them applicable in the fabrication of 2D and 3D patterns. Furthermore, the polymer films also showed high refractive indices, which were tunable upon exposure to UV light.

56 citations


Journal ArticleDOI
TL;DR: In this paper, fluorinated diblock copolymer micelles in chloroform were used to stabilize the templated water droplets in bulk, and also introduced as the water droplet stabilizer in other polymeric materials.
Abstract: Polymeric honeycomb microporous films were prepared from fluorinated diblock copolymers, poly(tert-butyl acrylate)-b-poly(2-[(perfluorononenyl)oxy]ethyl methacrylate) (PtBA-b-PFNEMAs), and four other commercial polymers, including polystyrene (PS), polycarbonate (PC), polylactic acid (PLA), and polymethylmethacrylate (PMMA) via breath figures method. The as-formed fluorinated diblock copolymer micelles in chloroform were not only utilized to stabilize the templated water droplets in bulk, but also introduced as the water droplets stabilizer in other polymeric materials. Our strategy was successfully achieved, as the micropores were decorated with the fluorinated diblock copolymer as directly shown in the SEM images and FT-IR/ATR-FTIR. Polymer concentration and the solution casting volume effects were checked to tune the sizes of the micropores in diblock copolymer films. The ratio of the added fluorinated diblock copolymer as a novel factor to tune the sizes of the micropores was also investigated.

26 citations


Journal ArticleDOI
TL;DR: In this paper, a fluorine-containing diblock copolymer, poly(tert-butylacrylate)-b-poly(2-[(perfluorononenyl) oxy] ethyl methacrylated) (PtBA-b-PFNEMA) in THF/water mixtures was prepared by dynamic self-assembly.
Abstract: Polymeric particles with diverse surface and internal hierarchical nanostructures were prepared by the dynamic self-assembly of a fluorine-containing diblock copolymer, poly(tert-butylacrylate)-b-poly(2-[(perfluorononenyl) oxy] ethyl methacrylate) (PtBA-b-PFNEMA) in THF/water mixtures. The surface patterns and internal structures both originated from the microphase separation of PtBA-b-PFNEMA and could be tuned by the preparation conditions. Besides, the interface limitations and geometric confinement of the particles' morphology resulted in the formation of different phase separation structures on the surface and inside the particles. By tuning the water content and preparation temperature, almost parallel cylindrical domains, twisted interconnected cylindrical domains, or spherical domains were obtained on the surface of the particles. Meanwhile, the internal structures of the particles transformed from inner stacked lamella with outer onion-like structures, inner disordered with outer onion-like structures, to bicontinuous structures as the chain mobility and incompatibility of the two blocks could be controlled by the preparation condition. Therefore, the integration of diverse cylindrical surface structures and bicontinuous or onion-like inner structures into hierarchical nanoparticles was achieved.

Journal ArticleDOI
TL;DR: In this paper, the surface properties of polyvinylidene fluoride (PVDF)/poly(methyl methacrylate) (PMMA) membranes are investigated and the surface property and blood compatibility of which are thoroughly investigated.
Abstract: Poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) membranes have important applications as biomaterials. In this study, PVDF/PMMA with varying ratios is blown into membranes, the surface property and blood compatibility of which are thoroughly investigated. Membrane surface characteristics including composition and topography exert considerable influence on the blood compatibility. Introduction of PMMA disturbs PVDF crystallization, however, favors the β phase crystal formation. PVDF content, crystallization ability, and surface enrichment have decisive effects on the membrane surface composition. Meanwhile, with increased PMMA fraction, the membrane surface roughness is also increased, and subsequently results in decreased hemocompatibility. While the membranes with PMMA content lower than 30 wt% show good blood compatibility, those with higher PMMA fraction exhibit obvious platelet adhesion to the surface. Thermal annealing promotes the formation of β phase PVDF and generates much smoother surface, thus endowing the membranes with greatly enhanced blood compatibility. These results show the prospect for optimization of processability, surface property, and blood compatibility of PVDF/PMMA membranes through facile modulation of PMMA content and fabrication process.

Journal ArticleDOI
TL;DR: In this paper, a magnetic field treated perfluorosulfonate ionomer (PFSI) membranes with improved through-plane proton conductivity are facilely fabricated though solvent casting of PFSI/Fe3O4 nanocomposite dispersion without any third additive under magnetic field followed by discarding the Fe3O 4 nanoparticles.

Journal ArticleDOI
TL;DR: The PFBI8 copolymer with 9,9'-dioctylfluorene and 2,2'-(1,4-phenylene)-bis(benzimidazole) moieties was synthesized through palladium-catalyzed Suzuki coupling reaction as discussed by the authors.
Abstract: Blue light-emitting materials are receiving considerable academic and industrial interest due to their potential applications in optoelectronic devices. In this study, blue light-emitting copolymers based on 9,9'-dioctylfluorene and 2,2'-(1,4-phenylene)-bis(benzimidazole) moieties were synthesized through palladium-catalyzed Suzuki coupling reaction. While the copolymer consisting of unsubstituted benzimidazoles (PFBI0) is insoluble in common organic solvents, its counterpart with N-octyl substituted benzimidazoles (PFBI8) enjoys good solubility in toluene, tetrahydrofuran, dichloromethane (DCM), and chloroform. The PFBI8 copolymer shows good thermal stability, whose glass transition temperature and onset decomposition temperature are 103 and 428 degrees C, respectively. Its solutions emit blue light efficiently, with the quantum yield up to 99% in chloroform. The electroluminescence (EL) device of PFBI8 with the configuration of indium-tin oxide/poly(ethylenedioxythiophene):poly( styrene sulfonic acid)/PFBI8/1,3,5-tris(1-phenyl-1H-benzimidazole-2-yl) benzene/LiF/Al emits blue light with the maximum at 448 nm. Such unoptimized polymer light-emitting diode (PLED) exhibits a maximum luminance of 1534 cd/m(2) with the current efficiency and power efficiency of 0.67 cd/A and 0.20 lm/W, respectively. The efficient blue emission and good EL performance make PFBI8 promising for optoelectronic applications. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 2172-2181, 2012


Journal ArticleDOI
TL;DR: In this article, the antiaging agent N,N′-di-2-naphthyl-p-phenylenediamine (DNP) was used to prevent the degradation of the ethylene tetrafluoroethylene alternating copolymers.
Abstract: It is generally accepted that ethylene tetrafluoroethylene alternating copolymers (ETFEs) are exceptionally thermal stable materials. However, we found that ETFEs will decompose to some extent when exposed to heat, especially above 300 °C and during a dynamic shear process (thermal mechanical degradation, thermal-stress-oxidation synergistic destruction). In this article, the dynamic mechanical degradation of ETFE was first verified by dynamic rheometry with the aid of IR analysis, then a facile, environmental friendly solution—namely the addition of the antiaging agent N,N′-di-2-naphthyl-p-phenylenediamine (DNP)—was adopted to prevent the degradation. Rotational rheometry and thermogravimetry analysis results proved that this is an applicable strategy. The addition of DNP led to remarkable increases in the initial thermal decomposition temperature, dynamic shear stable duration time, and thermal decomposition activation energy of ETFE without sacrificing its mechanical properties.


Journal ArticleDOI
TL;DR: In this article, a new method to prepare high quality PFSI membranes from their precursor solutions is developed, which exhibit better dimensional stability, higher proton conductivity, and remarkably decreased methanol crossover when compared with those of traditional membranes.
Abstract: A new method to prepare high quality PFSI membranes from their precursor solutions is developed. The obtained membranes exhibit better dimensional stability, higher proton conductivity, and remarkably decreased methanol crossover when compared with those of traditional membranes.

Journal ArticleDOI
TL;DR: In this paper, the fluorophilic interaction was introduced into the dynamic self-organized precipitation (D-SORP) method to control the phase behavior in polymeric particles.
Abstract: Co-assembly of poly(tert-butylacrylate)-b-poly(2-[(perfluorononenyl) oxy] ethyl methacrylate) (PtBA-b-PFNEMA, FA) and poly(ethyleneoxide)-b-poly(2-[(perfluorononenyl) oxy] ethyl methacrylate) (PEO-b-PFNEMAs, FB) were carried out to construct binary blend polymeric particles with diverse microphase structures through fluorophilic interaction. Successful control of the phase behavior relies on the location of FB within a nanoscale particle. Due to the fluorophilic interaction, FB is located at the interface between PtBA and PFNEMA or partly dissolved in the PFNEMA phase rather than forming an individual microdomain. By changing the composition of the binary blend particles, the water content, and preparation temperature and the fluorophilic interaction could be tuned and hence the location of FB could be influenced. Order–order phase transition and transformation from most stable onion-like lamellar structures to stacked lamellar structures and cylindrical structures were achieved utilizing PEO113-b-PFNEMA11 (FB1). In addition, the relatively shorter PFNEMA chain and larger dispersity (Đ) of PEO113-b-PFNEMA4 (FB2) resulted in the ubiquitously coexistence of ordered lamellar and gyroid microdomains in the same particles. These transitional structures, which were successfully obtained by both SEM and TEM, would be very useful for the investigation of the phase transition path. The introduction of fluorophilic interactions into the dynamic self-organized precipitation (D-SORP) method sustained the delicate control of the phase behavior in polymeric particles.

Journal ArticleDOI
TL;DR: In this paper, the authors explored the origin of poor processability of Teflonethylene/hexafluoropropylene copolymers in a rheological way, because melt rheology behaviors are highly related to their processing processes.
Abstract: Tetrafluoroethylene/hexafluoropropylene copolymers (FEPs) are widely used in diverse fields due to their outstanding performances in chemical resistance, thermal stability, and insulation. However, their processsability is poor, exhibiting narrow stable flow region and remarkably early melt fracture. Herein, we tried to explore the origin of such poor processability in a rheological way, because melt rheology behaviors are highly related to their processing processes. The shear rheology results indicate that FEPs exhibit multiple flow regions. The flow curve of FEP608 was obtained, and its η0 value was calculated to be 1.70 kPa s−1 at 360°C. Extensional rheological data suggest that FEPs have much lower e and B values when compared with those of common polymers, suggesting their weaker elasticity during extrusion. Based on such rheological results, the poor processability of FEPs is ascribed to their high viscosity induced by special interchain interaction associating with F atom, which can easily cause accumulated elastic energy. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Journal ArticleDOI
TL;DR: In this paper, a bluish green emitter with aggregation-induced emission activity and excellent electron-transport properties is presented. But the authors focus on the bluish-green emitter (I) only.
Abstract: synthesis and characterization of the new bluish-green emitter (I) with aggregation-induced emission activity and excellent electron-transport properties

Journal ArticleDOI
TL;DR: In this article, a perfluorodiacyl initiator, bis(perfluoro-2-n-propoxypropionyl) peroxide, in supercritical carbon dioxide was successfully prepared using a polytetrafluoroethylene (PTFE) homopolymers.
Abstract: Low-molecular-weight (Mn) polytetrafluoroethylene (PTFE) homopolymers were successfully prepared using a perfluorodiacyl initiator, bis(perfluoro-2-n-propoxypropionyl) peroxide, in supercritical carbon dioxide. Solid-state 19F NMR and Fourier transform infrared spectral analyses show that perfluoroalkyl end-groups are present in the resultant PTFEs. Thermogravimetric analysis suggests all polymers with various Mn have outstanding thermal stability. Differential scanning calorimetry measurements indicate that both melting and crystallization transitions of PTFE shift to lower temperatures when Mn decreases, because shorter polymer chains can move more easily at lower temperatures. Investigation of polymerization kinetics suggests that the rate law for the polymerization has kinetic orders of 0.5 and 1.0 with respect to initiator and monomer concentrations, indicating that termination occurs through coupling of propagating chains. Melt fusion crystallinity of as-polymerized PTFE can be as high as 86%, and the polymerization rate does not seem to be obviously affected by the total interphase area of the polymer phase, implying polymerization mainly occurs in the carbon dioxide-rich fluid phase; meanwhile, the low viscosity and high diffusivity of supercritical carbon dioxide mean that propagating chains have more opportunities to meet, thus yielding low-Mn PTFEs. Copyright © 2012 Society of Chemical Industry

Journal ArticleDOI
TL;DR: Tetrafluoroethylene (TFE) and perfluoropropylvinyl ether (PPVE) were copolymerized in supercritical carbon dioxide (sc-CO2) with bis(perfluoro-2-n-propoxypropionyl) peroxide (BPPP).
Abstract: Tetrafluoroethylene (TFE) and perfluoropropylvinyl ether (PPVE) were copolymerized in supercritical carbon dioxide (sc-CO2) with a perfluorodiacyl initiator bis(perfluoro-2-n-propoxypropionyl) peroxide (BPPP). The resultant copolymers with stable perfluoroalkyl end groups were obtained, avoiding the decomposition during processing and applications. Reactivity ratios of TFE and PPVE were first reported. The rTFE and rPPVE values are about 8 and 0.08, respectively. Such parameters are significant for the modification of PTFE through copolymerization of TFE and PPVE. It is found that through increasing the reaction pressure from 8.5 to 25 MPa, while rTFE increases by 12.0%, rPPVE decreases by 9.0%, which should be ascribed to the enhancement of the polarity of CO2 under high pressures. Because the reactivity of TFE is by two orders of magnitude higher than that of PPVE; on one hand, the copolymerization rate falls rapidly with the decrease of TFE feed ratio; on the other hand, TFE content in the copolymer decreases with the reaction time. All copolymers containing different fractions of PPVE enjoy outstanding thermal stability. The DSC result indicates that there exist two forms of crystals with highly regular molecular arrangement or less ordered chain packing which is disturbed by perfluoropropyl pendants. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Journal ArticleDOI
TL;DR: In this paper, the authors compared the performance of tetrafluoroethylene alternating copolymer (ETFE) and non-fluorinated polyethylenes (PE) under high-shear conditions and found that PE does not have sharkskin region or second smooth region.
Abstract: Flow behaviors and rheological properties of ethylene tetrafluoroethylene alternating copolymer (ETFE) under high-shear conditions were first reported. Flow instabilities, shear and extensional viscosities, and die swell of ETFE were investigated. Rheological behaviors of perfluorinated ethylene propylene copolymers (FEP), partially fluorinated ETFE, and non-fluorinated polyethylenes (PE) were compared for understanding the role of fluorine incursion on materials properties. It is found that (1) ETFE does not have sharkskin region or second smooth region which frequently occurs in FEP and linear PE; (2) critical shear stresses at which surface melt fracture occurs for the three polymers follow the order: FEP < ETFE < PE; (3) stable flow region narrows, die swell weakens, and flow activation energy increases when fluorine content of polymer increases. After time–temperature superposition, shifted shear viscosity, extensional viscosity, and elastic data (die swell) present universal scaling characteristic and superpose well in term of the same shift factors.

Journal ArticleDOI
TL;DR: In this article, a new method, namely supercritical carbon dioxide (Sc-CO2) treatment was developed to enhance the anti-cracking performance of PFSA membranes, which increased the increased crystallinity and reduced ionic clusters size of the ScCO2 treated membranes.
Abstract: Due to the outstanding stability, biocompatibility, and permeability, perfluorosulfonic acid (PFSA) membranes can be used to protect biosensors in biological environment. However, mineralization induced cracking hinders their in vivo applications for long duration. Various methods including anneal, preincubation in FeCl3 solution, and layer-by-layer self assembly were attempted to improve their anti-cracking performance, but only met with limited success. In this study, a new method, namely supercritical carbon dioxide (Sc-CO2) treatment was developed to enhance the anti-cracking performance of PFSA membranes. After being incubated in cell culture medium for 12 weeks, while the pristine membranes undergone intense cracking, their Sc-CO2 treated counterparts kept almost intact. Small-angle X-ray scattering and wide-angle X-ray diffraction results revealed the more perfect structure in the treated membranes. Meanwhile, the crystalline structure of pristine membranes was obviously destroyed after cultivation, whereas the treated membranes exhibited little change. The increased crystallinity and reduced ionic clusters size of the Sc-CO2 treated membranes are responsible to the greatly enhanced anti-cracking performance. In addition, such improvement paves the way for the applications of PFSA membranes in implantable biosensors.

Journal ArticleDOI
TL;DR: The excellent biocompatibility and anti-cracking performance of Na+-type PFCI membranes make them promising implantable biomaterials and protective layers in biosensors.
Abstract: Perfluorosulfonate ionomer (PFSI) membranes can be used to protect biosensors in biological environment. Perfluorocarboxylate ionomer (PFCI) has similar structure to PFSI, and is thus expected to be applicable in vivo. In this study, biocompatibility and anti-cracking performance of PFCI membranes were first investigated. Among various kinds of PFCI membranes, the Na+-type exhibited best blood compatibility, as evidenced by the human platelet adhesion and hemolysis rate experiments. When cultured on Na+-type PFCI membranes, endothelial cells spread and proliferated to colonize the entire surface, indicating good cell adhesion activity of the membranes. The Na+-type membranes were also subcutaneously implanted into guinea pigs, whose incisions were healed after operation without significant rejection phenomenon. After incubation in cell culture medium for 12 weeks, PFCI membranes kept intact only with trace amount of calcium phosphate deposition. XRD and SAXS results demonstrated that PFCI membranes possessed higher crystallinity and smaller ion cluster size than PFSI membranes, thereby endowing the membranes with much better anti-cracking performance. The excellent biocompatibility and anti-cracking performance of Na+-type PFCI membranes make them promising implantable biomaterials and protective layers in biosensors.

Journal ArticleDOI
TL;DR: In this paper, a homopolymerization of tetrafluoroethylene (TFE) in supercritical carbon dioxide (sc-CO2) initiated by bis(perfluoro-2-n-propoxypropionyl) peroxide (BPPP) was conducted.