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In recent years, several strategies have been proposed and demonstrated to enhance the efficiency of organic light-emitting diodes (OLEDs) and organic photovoltaics (OPVs). In both types of devices, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is commonly used to enhance hole injection. The layer is further designed by incorporating metallic-based, carbon-based, organic, inorganic, and hybrid nanoparticles with the aim of improving the performance and hence the efficiency through the improvement of light out-coupling in OLEDs and enhancement in light absorption generation of hole-charge carriers in OPVs. This review elucidates the use of different types of nanoparticles that are doped into PEDOT:PSS and their effects on OLEDs or OPVs. The effects include surface plasmon resonance (SPR), scattering, better charge transport, improvement in surface morphology and electrical properties of PEDOT:PSS. Promising results have been obtained and can potentially lead to low cost, large-area manufacturing process.

Compared with traditional thermosets, malleable thermosets have more applications in aerospace, biotechnology, and construction. Here we report a one-step, solvent-free, catalyst-free polycondensation method between diamine and formaldehyde to prepare a series of malleable hemiaminal dynamic covalent networks (HDCNs). The materials have excellent malleability and reprocessability by hot pressing. The Young’s modulus and breaking strength of HDCNs obtained by the polycondensation of formaldehyde and 4,4-diaminodiphenylmethane (MDA) are as high as 1.6 GPa and 60 MPa, respectively, which can be facilely adjusted through the introduction of polyetheramine-400 (PEDA). Moreover, the HDCNs feature the shape memory ability with a recovery ratio above 93.5% and can be recycled by the addition of different monomers. This promising HDCN, prepared from economical raw materials, may have vast applications in industries.

Colorless-to-colorful switching electrochromic polymers with very high contrast ratio are unattainable and attractive for the applications of smart wearable electronics. Here we report a facile strategy in developing colorless-to-colorful switching electrochromic polyimides by incorporating with alicyclic nonlinear, twisted structures and adjusted conjugated electrochromophores, which minimize the charge transfer complex formation. It is noted that, by controlling the conjugation length of electrochromophore, the colorless-to-black switching electrochromic polymer film (PI-1a) exhibites an ultrahigh integrated contrast ratio up to 91.4% from 380 to 780 nm, especially up to 96.8% at 798 nm. In addition, PI-1a film with asymmetric structure also demonstrates fast electrochemical and electrochromic behaviors (a switching and bleaching time of 1.3 s and 1.1 s, respectively) due to the loose chain stacking, which provides more pathways for the penetration of counterion. Moreover, the colorless-to-black EC device based on PI-1a reveals an overall integrated contrast ratio up to 80%., Electrochromic polymers (ECPs) receive great attention due to their facile colour tunablility, however colourless-to-black ECPs with high contrast ratio are still unattainable. Here the authors develop high contrast colourless-to-black switching polyimides by following specific molecular design criteria.

Polymeric vesicles show vast potential in drug delivery for the treatments of various diseases. In this work, we report here an advanced polymeric vesicle formed by amphiphilic bottlebrush block copolymers (BBCPs), which have a large size and can resist different kinds of surfactants in a degree. The amphiphilic BBCPs with controlled molecular weights and narrow molecular weight distributions were synthesized by ring-opening metathesis polymerization of norbornyl-poly (ethylene glycol) (NPEG) and norbornyl-trithiocarbonates (NTTA) followed by reversible addition-fragmentation chain transfer (RAFT) with styrene. GPC and 1HNMR were used to characterize BBCPs. Turbidity measurements, transmission electron microscopy, and scanning electron microscopy were used to explore the morphologies of the aggregation. Depending on the content of water added, many intermediate structures like compound vesicles and sphere could be found. After lyophilization, the BBCP vesicles happended a fusion and can retain vesicle morphology and show some stability in the presence of sodium dodecyl sulfate (SDS), hexadecyl trimethyl ammonium bromide (CTAB), Brij 78P and sodium chloride. This work serves a promising way to construct stable vesicles with BBCPs for biomedical applications.

Soluble aromatic polyimides and polyvinyls were prepared by incorporating pyridine moiety and its derivatives in the backbone and the side groups, respectively: 6F-Py-i polymers based on the polyimide backbone (6F-Py-1 to 6F-Py-7) and PVPy-i polymers based on the polyvinyl backbone (PVPy-1 to PVPy-4). All polymers were found to be amorphous. The 6F-Py-i polymers were thermally stable up to 511–545 °C; the PVPy-i polymers were stable up to 362–376 °C. Their glass transitions, thin film densities, molecular orbitals, and band gaps were determined. The electrical devices fabricated with the polymers in an electrode/polymer/electrode structure revealed p-type unipolar write-once-read-many times (namely, permanent) or dynamic random access memory or dielectric behavior, depending on the substituents of the pyridine unit and the film thicknesses. In particular, such digital memory characteristics were found to originate from the pyridine moieties possessing a high charge affinity in the polymers. However, the pyridine moieties were found to still need at least two or more aromatic substituents to get enough power to stabilize charges via utilizing the resonance effects provided by the substituents. Overall, this study demonstrated that the pyridine unit conjugated with two or more aromatic substituents is a very useful component to design and synthesize digital memory materials based on thermally stable polyimides and other high performance polymers. The 6F-Py-i polymers have potential for the low-cost mass production of high-performance programmable unipolar permanent memory devices with very low power consumption.

In this work, we present a novel pyrene-functionalized benzoxazine (Py-BZ)/single-walled carbon nanotubes (SWNTs) complex material as an efficient luminescent chemosensor for gaseous amines. It is shown that an interaction of poly(Py-BZ)/SWCNTs nanocomposites with analyte vapor leads to the increase of the intensity of luminescence. The response of these sensors to methylamines by static and dynamic flow measurement were studied.

In this study, a novel conjugated polymer, denoted as ECPblack, is synthesized. ECPblack demonstrated a unique electrochromic behavior with an ultrahigh contrast ratio (over 80%) in most of the visible regions, boasting an ultrahigh integrated contrast ratio of 71.8% between 380 nm and 880 nm. The long conjugated pendant group (pyrene) in ECPblack enhances the absorption in the blue region in its second oxidized state and results in transmissive-to-black electrochromic switching between the neutral state and the oxidized state. The transmissive-to-black electrochromic switching polymer with an ultrahigh contrast ratio could be especially attractive for applications in electronic displays. In addition, when polytriarylamine/nanotube (SWNT/P2) dispersion is doped in ECPblack, the response time of its electrochemical and electrochromic behaviors is further reduced. The electrochromic switching and bleaching time of SWNT/P2/ECPblack decreased by 73% and 80%, respectively. The improvement is caused by the phase separation of the rigid SWNT and the flexible polymer, which generates a rough surface morphology and provides more pathways for faster diffusion of counterions (ClO4−). The polymer/SWNT doping technique provides a simple way to accelerate ion diffusion in anodically coloring materials.

The organo-soluble and extremely stable polynorbornene PHNB-HPB with a hexaphenylbenzene (HPB) moiety was prepared by ring-opening metathesis polymerization (ROMP) followed by hydrogenation. The hexa-peri-hexabenzocoronene (HBC)-containing PHNB-HBC, which is insoluble in commercial organic solvents, was prepared by the cyclodehydrogenation of PHNB-HPB. The glass transition temperature of PHNB-HPB was 205 °C. The temperatures required for a 10% weight loss (Td10) for PHNB-HPB and PHNB-HBC were 428 °C and 456 °C under a nitrogen flow, respectively. The PHNB-HBC exhibited an ordered self-assembly in the solid state. The exfoliation of PHNB-HBC aggregates was tested by ultrasonication in various solvents. The PHNB-HBC dispersion solutions showed an intensive emission of the 0–0 transition (465 nm) due to the lower D6h symmetrical structure and alkoxy substituents. Between different solvents, the dispersion in N-cyclohexyl-2-pyrrolidone (CHP) showed the highest individual metric and the strongest 0–0 transition (465 nm), indicating higher dispersibility.

We report stable and efficient quasi-solid-state dye-sensitized solar cells (QS-DSSCs) fabricated using a combination of TiO2 nanoparticles and a low-molecular-mass organogelator (LMOG) as a nanoparticle–gel composite electrolyte. Three types of electrolyte, namely liquid, LMOG-based gel, and nanoparticle–gel composite, are used. The results of electrochemical impedance spectroscopy and intensity-modulated photocurrent/photovoltage spectroscopy measurements suggest that the presence of TiO2 nanoparticles in the nanoparticle–gel composite electrolyte could afford faster electron transport and a longer electron recombination time compared to the liquid and LMOG-based gel electrolytes. The QS-DSSC using the nanoparticle–gel composite electrolyte with the optimal TiO2 content exhibits a power conversion efficiency of 7.79%, which is significantly higher than that of devices using the liquid (7.22%) and LMOG-based gel (7.21%) electrolytes. Remarkably, the QS-DSSCs with the optimal nanoparticle–gel composite electrolyte exhibit long-term stability over 10 days, unlike the liquid electrolyte-based cells.

We propose a linkage approach by merging ambipolar electrochromic (EC) materials in both π-acceptor-π (π-A-π) and donor-acceptor-donor (D-A-D) configurations and investigated their electrochemical and spectroelectrochemical properties using density functional theory calculations. Here, we considered anthracene, toluene, and pyrene as π-conjugated molecules, triphenylamine (TPA) as a donor, and viologen as an acceptor moiety for π-A-π and D-A-D configurations. We have also explored the substitutional effects in the donor moiety on the overall electrochromism during both oxidation and reduction processes. Here, we mainly focused on the relationship between the structure, substitution of functional groups, electronic and spectral properties, as well as redox potential of the designed monomers. Our calculations indicate that the designed monomers have attractive absorption properties and show clear color switching upon the redox process. We find that the substitution of stronger electron-donating and π-spacer groups create new absorption peaks in the oxidation states. These designed viologen derivatives will be potential candidates, which can be used in both oxidation and reduction processes for upcoming EC devices.

In this work, polymers of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-triphenylamine] with side chains containing: pyrene (C1), diphenyl (C2), naphthalene (C3), and isopropyl (C6) structures were synthesized via a Suzuki coupling reaction. The structures were verified using NMR and cyclic voltammetry measurements provide the HOMO and LUMO of the polymers. The polymer with pyrene (C1) and naphthalene (C3) produced photoluminescence in the green while the polymer with the side chain containing diphenyl (C2) and isopropyl (C6) produce dual emission peaks of blue-green photoluminescence (PL). In order to examine the electroluminescence properties of the polymers, the solutions were spin-coated onto patterned ITO anode, dried, and subsequently coated with an Al cathode layer to form pristine single layer polymer LEDs. The results are compared to a standard PFO sample. The electroluminescence spectra resemble the PL spectra for C1 and C3. The devices of C2, C3, and C6 exhibit voltage-dependent EL. An additional red emission peak was detected for C2 and C6, resulting in spectra with peaks at 435 nm, 490 nm, and 625 nm. The effects of the side chains on the spectral characteristics of the polymer are discussed.

In this work, a water/alcohol-soluble conjugated polymer poly [(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9–dihexylfluorene)] (PFNC6) is synthesized and the photophysical properties are investigated. Subsequently, it is tested as electron injection layer in a blue emitting OLED with PFO. The maximum current efficiency (CE) and external quantum efficiency (EQE) of the device increased by 3 times to 0.75 cd/A and 0.66%. Further enhancement in the OLED performance is obtained when a bilayer electron injection consisting of PFNC6 and LiF are used where the maximum CE is 2.16 cd/A and the maximum EQE is 1.55%. Measurement with electron-only-devices confirmed that the electron mobility is increased for the device with PFNC6 as compared to the control device. Furthermore, higher Vbi is obtained in photovoltaic measurement when PFNC6 is used. As a result, the electron injection barrier is reduced and electron injection is more efficient.

A new approach for polytriarylamine (PTAA)-assisted selective dispersion for single-walled carbon nanotubes (SWNTs) in a toluene solution has been developed. The triarylamine-based conjugated polymers are able to selectively wrap the SWNTs with specific chiral indices depending on their backbone structures (e.g., PTAA12, PTAA12-P, and PTAA12-BP) and side-chain functionality (e.g., PTAA6, PTAA6-alt-PTAA, and PTAA12-alt-PTAA). PTAA12 exhibits highly selective wrapping for the (6,5) chirality from CoMoCAT (catalytic processes) SWNTs but low selectivity in a dispersion of HiPCO (high-pressure carbon monoxide) SWNTs. Therefore, the selection for HiPCO SWNTs has been further improved via PTAA12-alt-PTAA wrapping with alternating side chains and mainly exhibits a high affinity to (6,5) SWNTs with high chiral angles (≥24.5°). The wrapping conformation and binding energy of the polymer/(6,5) SWNTs were studied via molecular modeling, and the simulated results are in good agreement with the experimental data for th...

In this study, a new triphenylamine-alt-fluorene conjugated copolymer, HPBPYFL6, with hexaphenylbenzene (HPB) and pyrene as asymmetrical pendant groups was synthesized via Suzuki coupling polymerization. The conjugated polymer had a weight-average molecular weight of 5.8 × 104 g mol−1 with a polydispersity index of 2.5 characterized by gel permeation chromatography (GPC). HPBPYFL6 showed good solubility in common organic solvents such as NMP, THF, toluene and dichloromethane at 25 °C. In addition, HPBPYFL6 possessed a high glass transition temperature of 260 °C and a 10% weight-loss temperature of 503 °C in nitrogen. HPBPYFL6 bearing a pyrene moiety had a solvatochromic fluorescence shift from a green to an orange emission as the polarity of the solvent increased. Cyclic voltammetry of HPBPYFL6 films cast onto indium-tin oxide-coated glass (ITO-glass) exhibited two oxidation redox couples at an E1/2 value of 0.82 and 1.17 V versus Ag/Ag+ in an acetonitrile solution. The HPBPYFL6 film on graphene-coated PET had an E1/2 value of 0.24 and 1.12 V. Conjugated polymer films exhibited reversible electrochromic behaviour with a colour change from pale yellow to deep blue upon electrochemical oxidation and high absorbance in the near-infrared (NIR) region. The switching and bleaching times were 5.16 s and 3.12 s for 1231 nm and were 3.30 s and 3.74 s for 1030 nm of HPBPYFL6 on ITO-glass. The strong NIR electrochromic absorbance of HPBPYFL6 was attributed to intervalence charge transfer by the incorporation of the HPB moiety. This phenomenon was confirmed by chemical oxidation as the oxidant contents increased in the solution state. Furthermore, the electrochromic mechanism was interpreted by DFT calculation and the simulated NIR electrochromic spectra of model compound HPBPYFL are in good agreement with the experimental data.

A diamine containing heterocyclic pyridine and unsymmetrical carbazole substituents, 4-(9-ethyl-3-carbazole)-2,6-bis(4-aminophenyl)pyridine (CBAPP), was prepared for use in the synthesis of poly(pyridine-imide)s PI-1–8 by direct polycondensation with dianhydrides in N,N-dimethylacetamide (DMAc). The poly(pyridine-imide)s derived from the diamine are highly soluble in solvents such as N-Methyl-2-pyrrolidone (NMP) and DMAc at room temperature. Noncoplanar polyimide (PI-1) showed excellent solubility, high transparency, and high-performance mechanical properties. These polymers had relatively high glass transition temperatures and exhibited good thermal stability in both nitrogen (Td10 > 470 °C) and air (Td10 > 450 °C). The PI-3∼5 cannot form flexible and tough films due to the unsymmetrical carbazole moiety, rigid structure, and polar–polar interaction. However, through copolymerization technique these polymers (PI-6∼8) could be enhanced through the solubility, mechanical, and thermal properties. The optical properties included a strong orange fluorescence (540 nm) after protonation with acid. When the HCl concentration was increased, a new absorption band at approximately 350 nm appeared, and the intensity of the fluorescent peak at 380 nm observed in the neutral polymer solution decreased, along with the appearance of the new fluorescent peak at 540 nm. The poly(pyridine-imide)s presented here showed only slight fluorescence quenching in the presence of methanol. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 405–412

Electrochromic polymers are attractive materials with enormous potential in the rapidly developing area of plastic electronics due to their flexibility, low-power consumption, ease of processing and low processing cost. Electrochromic devices created with electrochromic polymers are likely to be alternatives or supplements to the conventional inorganic electrochromic devices, which face challenges of durability and electrochromic properties. Several novel electrochromic polyimides, polyamides, and polynorbornenes prepared via polycondensation, ring-opening metathesis polymerisation (ROMP), etc., are introduced in this article. These various polymer species exhibit high thermal stability and mechanical strength.

A series of metal free organic sensitizers have been designed and their optoelectronic properties for DSSC applications have been systematically investigated using density functional theory (DFT) and time dependent density functional theory (TD-DFT) methods. The role of donor/acceptor monomers on the electron donating/withdrawing abilities has been discussed and promising donor–acceptor combinations are screened. Based on this screening, some of novel metal free sensitizers have been designed and their electronic and spectral properties have been investigated using DFT/TDDFT methods. Our results show that the designed molecules are promising candidates to provide good performances as sensitizers in the DSSC applications.

In this study we prepared a new class of pyrene-functionalized benzoxazines (Py-BZ) through reactions of phenol, paraformaldehyde, and pyren-1-amine (Py-NH2) in toluene and EtOH. We prepared Py-NH2 through catalytic reduction of 1-nitropyrene (Py-NO2), which we had synthesized through electrophilic aromatic substitution of pyrene, using HNO3 as the nitration agent. 1H and 13C nuclear magnetic resonance spectroscopy and Fourier transform infrared (FTIR) spectroscopy confirmed the chemical structure of this new monomer; differential scanning calorimetry (DSC) and FTIR spectroscopy revealed the curing behavior of the Py-BZ polymers. The presence of the pyrene-functionalized benzoxazine enhanced the solubility of single-walled carbon nanotubes (SWCNTs) in THF, leading to the formation of highly dispersible Py-BZ/SWCNT organic/inorganic hybrid complex materials. Fluorescence emission spectroscopy revealed significant π–π stacking interactions between the Py-BZ and the SWCNTs in these complexes. In addition, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis revealed that incorporating the SWCNTs into the Py-BZ matrix significantly enhanced the thermal stability of the polymer after thermal curing.

A composite sorbent modified with fluorinated aromatic polyamide, for single-step isolation of DNA from biological mixtures is developed. The sorbent is prepared by the polymer deposition from solution onto the surface of porous silica. It is shown that the polymer coating with a thickness of 4 nm is formed not only on the outer surface of the carrier particles but also on the inner pore surfaces. It is found that the material produced largely retained porosity of the pristine support and the material is selective in a one-step separation of nucleic acids and proteins by passing the bacterial lysate through a sorbent. The degree of purification of the isolated preparations of DNA is sufficient to be used directly in PCR analysis.

The fabrication of block copolymer (BCP) vesicles with controlled membrane permeability and promising stability remains a considerable challenge. Herein, a new type of pH-responsive and self-crosslinked vesicle based on a hydrolytically hindered urea bond is reported. This kind of vesicle is formed by the self-assembly of a pH-responsive and hydrolytically self-crosslinkable copolymer poly(ethylene glycol)-block-poly[2-(3-(tert-butyl)-3-ethylureido)ethyl methacrylate-co-2-(diethylamino)ethyl methacrylate] (PEG-b-P(TBEU-co-DEA)). The BCP can be easily synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-(3-(tert-butyl)-3-ethylureido)ethyl methacrylate (TBEU) and 2-(diethylamino)ethyl methacrylate (DEA) using PEG-based macro-chain transfer agent. The copolymer could self-assemble into stable vesicles by the hydrophobic interaction and in situ cross-linking between amines and isocyanates after the hydrolysis of the hindered urea bonds without any catalyst. Dynamic light scattering (DLS) studies show that the vesicles exhibit enhanced stability against the dilution of organic solvent, and the size can be adjusted through the change of pH values. Moreover, the alkaline phosphatase-loaded vesicles can act as nano-reactor and enable free diffusion of small molecules into the vesicles, followed by the significantly improved fluorescence intensity of phosphate-caged fluorescein. This self-crosslinking and pH-sensitive vesicles may serve as a smart platform in controlled drug delivery and molecular reactor.

To improve the pervaporation performance in separating an aqueous ethanol solution, polyamide thin-film composite (TFC) membranes (m-tolidine-H-TMC/mPAN) were prepared through the interfacial polymerization reaction between trimesoyl chloride (TMC) and 2,2'-dimethylbenzidine hydrochloride (m-tolidine-H) on the surface of a modified polyacrylonitrile (mPAN) membrane. The effects of the feed ethanol concentration on the pervaporation performance and the durability of m-tolidine-H-TMC/mPAN TFC membranes were investigated. To choose the optimal mPAN membrane as the TFC substrate, the effect of hydrolysis time on the chemical properties and separation performance of an mPAN substrate was also studied. An appropriate hydrolysis time of 15 min was chosen to obtain the mPAN substrate due to the corresponding high permeation flux. The m-tolidine-H-TMC/mPAN TFC membrane exhibited a high pervaporation performance for ethanol dehydration. A positron annihilation lifetime spectroscopy experiment was used to estimate the mean free-volume radius of the m-tolidine-H-TMC polyamide selective layer, which lay between the radii of the water and ethanol molecules. © 2013 Society of Chemical Industry

A new diamine containing pyridine and carbazole groups was synthesized via a Chichibabin reaction and subsequent reduction; this compound was then used in the preparation of organo-soluble aramides (PA-a–i). The resultant polymers had high glass transition temperatures, which fell within the ranges of 271–287 °C, and Td10 at 510–535 °C in a nitrogen atmosphere. The pristine PA-a exhibited the maximum value in the UV–vis absorption spectrum at 307 nm, and this value shifted to 394 nm after protonation by HCl. When the emission of the polymer in THF solution was observed, the intensity of the emission peak at 420 nm decreased and the intensity of a new emission peak at 552 nm increased as the acid concentration increased. Additionally, the color of the polymer solution changed from blue to yellow after protonation. The intensity of the emission at 552 nm based on excimers increased as MeOH content increased. The color of polymer films also changed irreversibly from yellow, which was indicative of the neutra...

Polyamide thin-film composite (TFC) membranes were prepared by interfacial polymerization. The purpose is to improve the pervaporation performance of polyamide membranes in separating an aqueous ethanol solution. A novel amine monomer 2,2′-dimethylbenzidine hydrochloride (m-tolidine-H) was reacted with an acyl chloride monomer trimesoyl chloride (TMC) on the surface of a modified polyacrylonitrile (mPAN) membrane. The effects of the following interfacial polymerization conditions on the TFC membrane pervaporation performance were investigated: monomer concentration, immersion time of mPAN in aqueous m-tolidine-H solution, and interfacial polymerization (IP) time for reacting m-tolidine-H with TMC. Attenuated total reflectance Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the chemical structure and the morphology of the membranes, respectively. To probe the variation in the fine-structure of the polyamide active layer and the free volume depth profile in the TFC membranes, positron annihilation lifetime spectroscopy (PALS) experiments coupled to a variable monoenergy slow positron beam were conducted. The densest portion of the polyamide layer was at the interface of the two immiscible monomer solutions, as detected based on the smallest o-Ps annihilation lifetime at positron incident energies of 1 and 2 keV with 0.05 and 0.5 wt% TMC, respectively. A high pervaporation performance of 2191 g/m2h permeation flux and 99 wt% water content of permeate was delivered by the polyamide TFC membrane that was prepared by immersing the mPAN membrane in a 1.5 wt% aqueous m-tolidine-H solution for 10 s, followed by contacting it with a 0.05 wt% organic TMC solution for 10 s.

The effect of chemical composition and morphology of the surface layers of new polyaramide-containing sorbents on the mechanism of selective sorption of nucleic acids and proteins was investigated as compared to the previously studied sorbents modified with fluoropolymers and polyaniline (high-throughput materials providing one-step isolation of DNA from biological mixtures). A series of silica-based sorbents modified with polyaramides having consistently varying structure and containing the set of "key" structural elements (aromatic units and nitrogen atoms in the backbone, fluorinated groups), and various donor and acceptor moieties was prepared. The chemical composition of the polymer coatings was evaluated by X-ray photoelectron spectroscopy. The surface morphology was studied by scanning probe microscopy. The sorption properties were investigated by passing the mixtures containing DNA, RNA and proteins of different nature through the cartridges containing the obtained sorbents. All the investigated materials weakly retain double-stranded DNA but effectively retain RNA and proteins. The sorption capacity of the sorbents depends on the protein nature. The observed sorption behavior was shown to be determined by the chemical structure and not by the morphology of the polymer coating. It was proposed that similarity of the sorption properties of the series of chemically different polymers could be determined by similar total input of different sorption mechanisms.

Novel conjugated polymers such as poly(phenylene-fluorene) P1 and poly(triphenylbenzene-fluorene) P2 with hexaphenylbenzene (HPB) as a pending side group were prepared by Suzuki coupling using the dibromo monomers M1 and M2 with 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester, respectively. The HPB moiety of P1 and P2 can be oxidatively cyclodehydrogenated with FeCl3 in nitromethane, yielding polymers P3 and P4 with hexa-peri-hexabenzocoronene (i.e., nanographene) units. The cyclodehydrogenation of nanographene-containing polymers was confirmed by FT-IR spectroscopy. In addition, X-ray powder diffraction of both P3 and P4 revealed a polymer interlayer spacing of 1.3 nm being dominated by the nanographenes. The glass transition temperatures (Tgs) of P1 and P2 were 202 °C and 235 °C, respectively, while both P3 and P4 with nanographenes possessed Tgs higher than 300 °C. Compared to P3, P4 with a triphenylbenzene moiety in its backbone can be well dispersed without aggregation in N-cyclohexyl-2-pyrrolidone (CHP), as confirmed by UV-Vis spectroscopy, photoluminescence spectroscopy (PL) and photoluminescence-excitation (PLE) maps.

A small organic molecule of 2,3-bis(5-bromothiophene-2-yl)acrylonitrile (DTDBAL) was synthesized for the first time and introduced into an active layer consisting of poly-3-hexylthiophene (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), in order to improve the performance of an inverted bulk heterojunction organic photovoltaic. The short-circuit current of the device was improved owing to the formation of a cascade band alignment of P3HT/DTDBAL/PCBM which enhanced the exciton dissociation and charge transport. Meanwhile, the open-circuit voltage and fill factor were simultaneously improved due to the optimization of the active layer morphology. The best power conversion efficiency achieved was 3.45% under simulated AM 1.5G illumination of 100 mW/cm 2 , which is an increase of 36% compared to a solar cell without the additive and featuring only P3HT/PCBM as the active layer.

In this paper, we demonstrated the successful synthesis of newly designed copolymers, C1 and C2, with donor-acceptor type structure. Both C1 and C2 copolymers contained 9,9-dioctylfluorene-2,7-bis(trimethyleneboronate) as one constructional unit to improve the solubility in common organic solvents. The other constructional unit was 2,3-bis(5-bromothiophen-2-yl)acrylonitrile (DTDBAL) for C1, while 4,7-dibromobenzo[c][1,2,5]thiadiazole unit, 5,5'-dibromo-2,2'-bithiophene unit and N1, N1-bis(4-bromophenyl)-N4,N4-bis(4-(2-phenylpropan-2-yl)phenyl)benzene-1,4-diamine are for C2. We fabricated photovoltaic devices based on the C1 and the C2 copolymers with Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer, PC70BM layer, TiOx layer, and aluminum (Al) electrode. The bulk heterojuntion photovoltaic devices using these copolymers as electron donor and PC70BM as the acceptor exhibited good device performances when measured at 100 mW cm-2. The power conversion efficiency (PCE) of the C1 device reached 0.45% with Voc, Jsc and FF of 0.51, 2.50 and 35%, respectively. The PCE of the C2 device reached 0.34% with Voc, Jsc, and FF of 0.56, 2.01 and 30%, respectively.

Polyimides rank among the most heat-resistant polymers and are widely used in high temperature plastics, adhesives, dielectrics, photoresists, nonlinear optical materials, membrane materials for separation, and Langmuir–Blodgett (LB) films, among others. Additionally, polyimides are used in a diverse range of applications, including the fields of aerospace, defense, and opto-electronics; they are also used in liquid crystal alignments, composites, electroluminescent devices, electrochromic materials, polymer electrolyte fuel cells, polymer memories, fiber optics, etc. Polyimides derived from monomers with noncoplanar (kink, spiro, and cardo structures), cyclic aliphatic, bulky, fluorinated, hetero, carbazole, perylene, chiral, non-linear optical and unsymmetrical structures have been described. The syntheses of various monomers, including diamines and dianhydrides that have been used to make novel polyimides with unique properties, are reported in this review. Polyimides, with tailored functional groups and dendritic structures have allowed researchers to tune the properties and applications of this important family of high-temperature polymers. The synthesis, physical properties and applications of advanced polyimide materials are described.

A new electrochromic norbornene derivative (NB) containing symmetrical diphenylamine and unsymmetrical triphenylamine groups, was synthesised from norbornene amine and unsymmetrical triphenylamine-substituted bromide. NB was used to obtain unsaturated PNB via ring-opening metathesis polymerization using different Grubbs' catalysts, followed by hydrogen reduction to obtain saturated HPNB. PNB and HPNB were highly soluble in common organic solvents such as toluene, xylene, benzene, chlorobenzene, 1,2-dichlorobenzene, and tetrahydrofuran at room temperature. The glass transition temperatures ( T g ) of PNB and hydrogenated HPNB were 162 °C and 117 °C, respectively. The 10% weight-loss temperatures of PNB and hydrogenated HPNB were 410 °C and 450 °C, respectively. Cyclic voltammogram of HPNB film cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited three reversible oxidation redox couples at 0.52, 0.85 and 1.30 V versus Ag/Ag + in acetonitrile solution. The electrochromic characteristics of HPNB showed excellent stability and reversibility, with multi-staged colour changes from light yellow to green, dark-blue and purple as the potential changed from 0 to 1.35 V. The colour switching time and the bleaching time of the HPNB were 8.7 s and 4.3 s, respectively, at 1084 nm and 7.9 s and 3.8 s at 879 nm.

Novel electrochromic polynorbornenes poly(NBPYTPAM) and poly(HNBPYTPAM), containing electroactive chromophores, were prepared via ring-opening metathesis polymerization (ROMP) from a new norbornene derivative (NBPYTPAM) using Grubbs’ catalyst and followed by hydrogen reduction. The glass transition temperatures (Tg) of poly(NBPYTPAM) and hydrogenated poly(HNBPYTPAM) were 190 and 175 °C, respectively. The cyclic voltammogram of the poly(HNBPYTPAM) film cast onto flexible graphene-coated polyethylene terephthalene (PET) substrates exhibited two reversible oxidation redox couples at 1.0 and 1.9 V. Flexible electrochromic devices were fabricated from the electroactive polymers and graphene-coated PET substrates. The electrochromic characteristics of poly(HNBPYTPAM) showed excellent stability and reversibility, with multistaged color changes from its yellow neutral form to green and then to dark-blue.

This study describes the utilization of a novel conjugated copolymer, namely, poly[2,3-bis(thiophen-2-yl)-acrylonitrile-9,9′-dioctyl-fluorene] (FLC8) for organic solar cell application for the first time. The highest occupied molecular orbital and the lowest unoccupied molecular orbital of FLC8 are −5.68 and −3.55 eV, respectively, which lie between the corresponding values of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methylester (PCBM). In addition, both electron and hole mobilities of FLC8 are in the range of 10−4 (cm2/V s), making it an excellent ambipolar polymer. Such unique properties make FLC8 a good candidate to form a ternary cascade bulk-heterojunction organic solar cell when blending with P3HT and PCBM. The power conversion efficiency (PCE) of the ternary cascade solar cell can be increased by up to 30% as compared with the reference cell without FLC8. We suspect that this enhancement of PCE is caused by the additional charge separation offered by the cascade structure and the fast charge transfer due to the ambipolarity of FLC8.

A high-glass-transition-temperature polynorbornene, poly(NBEDPY), containing chromophore groups was synthesized by ring-opening metathesis polymerization (ROMP) using Grubbs' catalysts; poly(HNBEDPY) was obtained by the reduction of poly(NBEDPY). The glass transition temperatures (Tg) of poly(NBEDPY) and hydrogenated poly(HNBEDPY) were as high as 250 °C and 220 °C, respectively, because of the rigid dipyrene groups, which are higher than those of commercially available ring-opened hydrogenated polynorbornenes (JSR ARTON®; 120–165 °C). The 10% weight-loss temperatures of hydrogenated poly(HNBEDPY) and poly(NBEDPY) were up to 450 °C and 400 °C, respectively. A hydrogenated poly (HNBEDPY) film showed excellent transparency (over 91%). The photoluminescence emission spectra of poly(HNBEDPY) showed strong solvent-polarity dependence, revealing that poly (HNBEDPY) underwent remarkable bathochromic shifts with an increase in solvent polarity. Poly(HNBEDPY) also showed remarkable fluorescent solvatochromism (blue in toluene, greenish yellow in dimethyl sulfoxide). The cyclic voltammogram of poly(HNBEDPY) film cast onto an indium tin oxide (ITO)-coated glass substrate exhibited one reversible oxidation redox couple at 0.55 V versus Ag/Ag+ in acetonitrile solution. The electrochromic characteristics of poly(HNBEDPY) showed reversibility, with a color change from its green neutral form to dark red upon the application of potentials from 0 to 1.0 V. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

A new electrochromic norbornene derivative containing triphenylamine groups (NBDTPAC8) was synthesized using norbornene amine and bromotriphenylamine. NBDTPAC8 was used in ring-opening metathesis polymerization to obtain poly(NBDTPAC8) using different Grubbs' catalysts and followed by hydrogen reduction to obtain poly(HNBDTPAC8). The glass transition temperatures (Tg) of poly(NBDTPAC8) and hydrogenated poly(HNBDTPAC8) were 132 and 89 °C, respectively. Poly(HNBDTPAC8) film exhibited a fluorescence maximum around 416 nm with a quantum yield of up to 60%. Hydrogenated poly(HNBDTPAC8) film showed excellent transparency (up to 93%). Poly(HNBDTPAC8) showed cyclic voltammetric and electrochromic behaviors similar to those of poly(NBDTPAC8). The cyclic voltammogram of a poly(HNBDTPAC8) film cast onto an indium tin oxide (ITO)-coated glass substrate exhibited three reversible oxidation redox couples at 0.69, 0.94 and 1.38 V versus Ag/Ag+ in an acetonitrile solution. The electrochromic characteristics of poly(HNBDTPAC8) showed excellent stability and reversibility, with multi-staged color changes from its colorless neutral form to green, light blue and dark blue upon the application of potentials ranging from 0 to 1.60 V. The color switching time and bleaching time of the poly(HNBDTPAC8) film were 6.2 s and 4.3 s at 1175 nm and 6.6 s and 4.4 s at 970 nm, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

To improve the pervaporation performance of thin-film composite membranes, novel thin-film composite membranes were prepared via interfacial polymerization by reacting 5-nitrobenzene-1,3-dioyl dichloride (NTAC) or 5-tert-butylbenzene-1,3-dioyl dichloride (TBAC) with triethylenetetraamine (TETA) on the surface of a modified polyacrylonitrile (mPAN) membrane (TETA-NTAC/mPAN and TETA-TBAC/mPAN). The effect of the acyl chloride monomers chemical structure on the pervaporation separation of an aqueous ethanol solution was investigated. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle measurements were applied to analyze the chemical structure, surface chemical composition, surface roughness and hydrophilicity of the polyamide active layer of the composite membrane. To correlate the variations in the free volume of the polyamide active layers with the pervaporation performance, positron annihilation spectroscopy (PAS) experiments were performed with a variable monoenergetic slow positron beam. From the results of the PAS and XPS experiments, the S parameter, o-Ps annihilation lifetime τ 3 (corresponding to free volume size) and its intensity I 3 (corresponding to free volume concentration), the τ 3 and I 3 of TETA-NTAC polyamide layer (positron incident energy of 1–1.7 keV) were both higher than those of TETA-TBAC polyamide layer. The S parameter for TETA-NTAC polyamide layer was also higher than that of the TETA-TBAC polyamide layer even though the former was more crosslinking than that of the latter. In the aqueous ethanol solution dehydration experiments, the TETA-NTAC/mPAN membrane produced both a higher permeation rate and water concentration in the permeate than the TETA-TBAC/mPAN membrane.

Novel bi-triphenylamine-containing aromatic dibro- mide M3, N,N-bis(4-bromophenyl)-N 0 ,N 0 -dipheny-l,4-phenylene- diamine, was successfully synthesized. The novel conjugated polymer P1 having number-average molecular weight of 1.31 � 10 4 was prepared via Suzuki coupling from the dibromide M3 and 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propane- diol) ester. Polymer P1 had excellent thermal stability associ- ated with a high glass-transition temperature (Tg ¼ 141 � C). The hole-transporting and UV-vis-near-infrared electrochromic properties were examined by electrochemical and spectroelec- trochemical methods. Cyclic voltammograms of the conjugated polymer films cast onto indium-tin oxide-coated glass sub- strates exhibited two reversible oxidation redox couples at E1/2 values of 0.73 and 1.13 V versus Ag/Ag þ in acetonitrile solu- tion. The hole mobility of the conjugated polymer P1 revealed � 10 � 3 cm 2 V � 1 s � 1 , which is much higher than that of other conjugated polymer systems. The observed UV-vis-near- infrared absorption change in the conjugated polymer film P1 at applied potentials ranging from 0.00 to 1.23 V are fully reversible and associated with strong color changes from pale yellowish in its neutral form to green and blue in its oxidized form. Using a combination of experimental study and theo- retical investigation, we proposed an oxidation mechanism based on molecular orbital theory, which explains the cyclic voltammetry experimental results well. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4654- 4667, 2010

A series of novel organosoluble polyimides and copolyimides with a propeller-shaped triarylamine unit were prepared from diamine and various aromatic dianhydrides via direct polycondensation. All of the polymers possessed tough, flexible, and strong films with high molecular weights. The polyimide and copolyimide films revealed electrochromic characteristics, with a color change from pale yellowish at its neutral state, to green, and finally to blue at its oxidized state, at applied potentials ranging from 0 to 1.50 V. The polyimide (Ib) film exhibited switching times of 4.5 s at 1.08 V at 424 and 877 nm and 1.9 s for fast bleaching due to a pendent substituted 2-phenyl-2-isopropyl group. Cyclic voltammetry (CV) of the polymer films showed two reversible redox couples at potentials of 0.91–0.99 V and 1.30–1.38 V, respectively. The CV results of the model compound M1 and model polyimide M2, were not a match to the oxidation peaks of polyimide Ib, indicating that the contribution of the oxidation was not only from the electron removal of nitrogen atoms.

A new rapid switching near-IR electrochromic conjugated propeller-shape polymer (PBTPAFL) with lower oxidation potential containing a di-triarylamine group was synthesized via Suzuki coupling approach. The observed UV-vis-NIR absorption changes in the PBTPAFL film at various potentials are fully reversible and associated with strong color changes from the original light green to dark green and then to a Prussian blue. Excellent continuous cyclic stability of the electrochromic characteristics with a rapid color switching time 2.58 s and bleaching time 1.76 s was found as well. Compared with P1 and P2, the introduction of more electron-donating propyl phenyl group in the para position of PBTPAFL lowered the oxidative potential and prevented coupling reaction during the electrochromic procedure. The high molecular weight conjugated polymer having high thermal stability with T d10 more than 450 °C has excellent solubility in common organic solvents such as NMP, THF, chloroform, toluene, xylene, and benzene at room temperature (25 °C) due to the propeller-shape structure and long alkyl chain on fluorene. Herein, from the combination of the experimental and computational study, we proposed a mechanism on the basis of the molecular orbital theory to explain the electrochromic oxidation behavior.

High-performance thin-film composite polyamide membranes for pervaporative dehydration processes were prepared by means of the interfacial polymerization of triethylenetetramine (TETA) and trimesoyl chloride (TMC) on the surface of a modified polyacrylonitrile (mPAN) membrane support. The effects of annealing processes applied during and after the composite membrane preparation on the pervaporation performance were investigated. Two annealing processes were applied. One was to the composite membrane formed after the interfacial polymerization by subjecting it to different annealing temperatures and the other to the aqueous amine (TETA) solution used during the interfacial polymerization process by varying its temperature. Positron annihilation spectroscopy experiments using a slow positron beam were carried out. One of the positron annihilation techniques, Doppler broadening energy spectroscopy (DBES), was used to study the effect of the annealing processes on the S parameter (corresponding to the free volume in the membrane). The first plateau (S1 = 0.47798 ± 1.86E−4, L1 = 182 ± 84 nm) in the curve obtained for the polyamide layer in the Type-B composite membrane was higher than that (S1 = 0.47659 ± 2.74E−4, L1 = 196 ± 52 nm) in the Type-A composite membrane. In other words, this corresponds to a higher S parameter and a thinner layer for the Type-B membrane than the Type-A membrane. This implies that the free-volume amount in the former membrane is higher than that in the latter. It was found that these two annealing processes greatly improved the pervaporation separation performances of the thin-film composite polyamide membranes prepared in this study in dehydrating aqueous alcohol solutions.

To investigate the variation in the fine structure of polyamide thin-film composite (TFC) membranes prepared via two different interfacial polymerization conditions (IP-I and IP-II), experiments on Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), water contact angle, and positron annihilation spectroscopy (PAS) coupled to a slow positron beam were conducted. Polyamide TFC membranes were prepared via the interfacial polymerization reaction between triethylenetetramine (TETA) and trimesoyl chloride (TMC) on the surface of a modified polyacrylonitrile (mPAN) membrane. Compared with the polyamide TFC membrane prepared via IP-I, the polyamide layer prepared via IP-II showed a shorter S plateau length (thinner thickness), a higher o-Ps intensity I3 value (higher free-volume concentration), and a smaller o-Ps lifetime τ3 value (smaller free-volume size), resulting in higher permeation rate and separation factor obtained from the pervaporative separation of a 70 wt% isopropanol aqueous solution at 25 °C.

A novel dibromo compound containing unsymmetrical substituted bi-triarylamine was synthesized. A conjugated polymer was prepared via the Suzuki coupling from the newly prepared dibromo compound and 9,9-dioctylfluorene-2,7-bis(tri-methyleneboronate). The glass transition temperature (T g ) of the conjugated polymer was 140 °C, 10% weight-loss temperatures (T d10 ) in nitrogen was 458 °C, and char yield at 800 °C in nitrogen higher than 64%. Cyclic voltammogram of the polymer film cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.70 and 1.10 V versus Ag/Ag + in acetonitrile solution. The polymer films revealed excellent stability of electrochromic characteristics, with a color change from yellow green of the neutral form to the dark green and blue of oxidized forms at applied potentials ranging from 0 to 1.3 V. The color switching time and bleaching time were 4.25 and 7.22 s for 860 nm and 5.51 s and 6.48 s for 560 nm.

A novel N,N,N′,N′-tetraphenyl-1,4-phenylenediamine (TPPA)-containing aromatic dibromide (3), N,N-bis(4-bromophenyl)-N′,N′-bis(4-(2,4,4-trimethylpentan-2-yl)phenyl)-1,4-phenylenediamine, was successfully synthesized. The novel conjugated polymer (4) having number-average molecular weight of 2.05 × 104 was prepared via Suzuki coupling from the dibromide (3) with 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester. The conjugated polymer (4) exhibited excellent solubility in common organic solvents such as N-methyl-2-pyrrolidinone (NMP), tetrahydrofuran, chloroform, and toluene at room temperature. The conjugated polymer (4) had useful levels of thermal stability associated with their relatively high glass transition temperature (Tg = 144 °C), 10% weight-loss temperatures (Td10) in nitrogen (Td10 = 445 °C), and char yields at 800 °C in nitrogen (59.0%). The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms o...

Tristable electrical conductivity switching and non-volatile memory effects are demonstrated in a conjugated copolymer of poly(2,6-diphenyl-4-((9-ethyl)-9 H -carbazole)-pyridinyl- alt -2,7-(9,9-didodecyl)-9 H -fluorenyl) (PPCzPF). The indium–tin oxide (ITO)/PPCzPF/Al device can be switched from the low-conductivity (off) state to the first high-conductivity (on-1) state at 1.8 V, with an on/off current ratio of approximately 100. The device can be further switched from the on-1 state to the next higher conductivity (on-2) state at 2.4 V, with an on-2/on-1 current ratio of approximately 20. All the three conductivity states are accessible, stable and non-erasable. The tri-level conductance switching can be explained in terms of field-induced conformational ordering of the polymer chains and enhanced charge-transfer interaction at the PPCzPF/ITO interface.