Surface properties and electrical charges are critical factors elucidating cell interactions on biomaterial surfaces. The surface potential distribution and the nanoscopic and microscopic surface elasticity of organic polypyrrole-hyaluronic acid (PPy-HA) were studied by atomic force microscopy (AFM) in a fluid environment in order to explain the observed enhancement in the attachment of human adipose stem cells on positively charged PPy-HA films. The electrostatic force between the AFM tip and a charged PPy-HA surface, the tip-sample adhesion force, and elastic moduli were estimated from the AFM force curves, and the data were fitted to electrostatic double-layer and elastic contact models. The surface potential of the charged and dried PPy-HA films was assessed with Kelvin probe force microscopy (KPFM), and the KPFM data were correlated to the fluid AFM data. The surface charge distribution and elasticity were both found to correlate well with the nodular morphology of PPy-HA and to be sensitive to the electrochemical charging conditions. Furthermore, a significant change in the adhesion was detected when the surface was electrochemically charged positive. The results highlight the potential of positively charged PPy-HA as a coating material to enhance the stem cell response in tissue-engineering scaffolds.

Polyaniline spherical and cubic shells with hierarchical nanostructures were prepared by using MnO(2) hollow hierarchical nanostructures with different morphologies as reactive templates in a controlled manner. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) images reveal that the PANI shells as-prepared are narrowly dispersed and possess uniform morphologies. Fourier transform infrared (FT-IR) and UV-vis spectra of the hollow shells indicate that the PANI exists in the emeraldine form. Cyclic voltammogram shows that the PANI exhibits multiple redox behavior during potentiodynamic cycling in acidic media at potentials. This strategy developed can be extended to synthesize other conducting polymers such as PPY shells with the similar controlled 3D hierarchical nanostructures.

A novel and facile method was developed to prepare a visible-light driven TiO2 /Ag-AgCl@polypyrrole (PPy) photocatalyst with Ag-AgCl nanoparticles supported on TiO2 nanofibers and covered by a thin PPy shell. During the synthesis, the PPy shell and Ag-AgCl nanoparticles were prepared simultaneously onto TiO2 nanofibers, which simplified the preparation procedure. In addition, because Ag-AgCl aggregates were fabricated via partly etching the Ag nanoparticles, their size was well controlled at the nanoscale, which was beneficial for improvement of the contact surface area. Compared with reference photocatalysts, the TiO2 /Ag-AgCl@PPy composite exhibited an enhanced photodegradation activity towards rhodamine B under visible-light irradiation. The superior photocatalytic property originated from synergistic effects between TiO2 nanofibers, Ag-AgCl nanoparticles and the PPy shell. Furthermore, the TiO2 /Ag-AgCl@PPy composite could be easily separated and recycled without obvious reduction in activity.

Conducting polypyrrole (PPy) nanotube arrays, nanotube networks and irregular films are deposited on biomedical titanium. By in situ application of weak periodic potentials, the nanostructured conducting polymers undergo a reversible switch in wettability, which is a redox process of dopant molecules (as hydrophilic groups) immobilized and de-immobilized on the surface of the conducting polymers.

Direct conversion of the tremendous and ubiquitous low-grade thermal energy into electricity by thermogalvanic cells is a promising strategy for energy harvesting. The environment is one of the richest and renewable low-grade thermal source. However, critical challenges remain for all-day electricity generation from environmental thermal energy due to the low frequency and small amplitude of temperature fluctuations in the environment. In this work, we report a tandem device consisting of a polypyrrole (PPy) broadband absorber/radiator, thermogalvanic cell, and thermal storage material (Cu foam/PEG1000) that integrates multiple functions of heating, cooling, and recycling of thermal energy. The thermogalvanic cell enables continuous utilization of environmental thermal energy at both daytime and nighttime, yielding maximum outputs as high as 0.6 W m^-2 and 53 mW m^-2, respectively. As demonstrated outdoors by a large-scale prototype module, this design offers a feasible and promising approach to all-day electricity generation from environmental thermal energy.

Protons from water are reduced by a catalytic system composed of a heteroleptic iridium(III) photosensitizer [Ir(ppy)2(bpy)]+, platinum catalyst, and sacrificial reductant. The hydrogen quantum yield reaches 0.26 in this study, which proceeds via reductive quenching of the excited photosensitizer by triethanolamine. This simplified approach allows the characterization of degradation products that are otherwise obscured in more complex systems. A novel 16-well setup for parallel kinetic analysis of H2 evolution enables high-throughput screening of reaction conditions and quantization of the decaying reaction rate. DFT calculations rationalize the differences between this and previous studies on tris-diimine ruthenium(II) photosensitizers.

Highly conductive free standing polypyrrole (PPy) films were prepared by a novel freezing interfacial polymerization method. The films exhibit metallic luster and electrical conductivity up to 2000 S cm(-1). By characterizing with SEM, FTIR, Raman and XRD, the high conductivity is attributed to the smooth surface, higher conjugation length and more ordered molecular structure of PPy.

This study described the possibility of using chemically modified chitin with polypyrrole (PPy-g-Ch) as an adsorbent for the removal of Pb(II) and Cd(II) ions from aqueous solution. The PPy-g-Ch was characterized using FTIR, SEM, EDX, XRD, TGA and DSC techniques. The influence of various parameters such as pH, dosage, co-ions, contact time and concentration on the removal of Pb(II) and Cd(II) ions was investigated. Among the various isotherm models studied, the Freundlich isotherm model fitted well to the equilibrium data. The magnitude of ΔG(0), ΔH(0) and ΔS(0) indicated the feasibility, spontaneity and the endothermic nature of the adsorption process, respectively. The kinetic process followed the pseudo-second-order kinetic model. The applicability of the PPy-g-Ch has been tested for the removal of Pb(II) and Cd(II) ions from a real water sample spiked with Pb(II) and Cd(II) ions.

Solar steaming has emerged as a promising green technology that can address the global issue of scarcity of clean water. However, developing high-performance, cost-effective, and manufacturable solar-steaming materials, and portable solar steaming-collection systems for individuals remains a great challenge. Here, a one-step, low-cost, and mass-producible synthesis of polypyrrole (PPy) origami-based photothermal materials, and an original portable low-pressure controlled solar steaming-collection unisystem, offering synergetic high rates in both water evaporation and steam collection, are reported. Due to enhanced areas for vapor dissipation, the PPy origami improves the water evaporation rate by at least 71% to 2.12 kg m^-2 h^-1 from that of a planar structure and exhibits a solar-thermal energy conversion efficiency of 91.5% under 1 Sun. When further controlling the pressure to ≈0.17 atm in the steaming-collection unisystem, the water collection rate improves by up to 52% systematically and dramatically. Although partial energy is utilized toward obtaining low-pressure, evaluations show that the overall energy efficiency is improved remarkably in the low-pressure system compared to that in ambient pressure. Furthermore, the device demonstrates effective decontamination of heavy metals, bacteria, and desalination. This work can inspire new paradigms toward developing high-performance solar steaming technologies for individuals and households.

2-Phenylpyrimidine skeleton-based multifunctional electron-transport materials are designed and synthesized. By using these materials and green phosphorescent emitter, fac-tris(2-phenylpyridine)iridium [Ir(ppy)(3)], extremely efficient green organic light-emitting devices are developed. The devices show the efficiencies of 128 lm W(-1) (105 cd A(-1)) at 100 cd m(-2) and 96 lm W(-1) (99 cd A(-1)) at 1000 cd m(-2).

Here, we report the synthesis of a luminescent ion pair with the formula [Ru(dtBubpy)3][Ir(ppy)2(CN)2]2. The crystal structure of this three component, heterometallic assembly is described, along with the luminescence properties of the salt. The modulation of the energy transfer between the blue-green-emitting iridium complex and the red-emitting ruthenium complex is also discussed as a function of both medium and concentration.

The excited states of fac-tris(phenylpyridinato)iridium [Ir(ppy)3] and the smaller model complex Ir(C3H4N)3 are computed using a number of high-level ab initio methods, including the recently implemented algebraic diagrammatic construction method to third-order ADC(3). A detailed description of the states is provided through advanced analysis methods, which allow a quantification of different charge transfer and orbital relaxation effects and give extended insight into the many-body wave functions. Compared to the ADC(3) benchmark an unexpected striking difference of ADC(2) is found for Ir(C3H4N)3, which derives from an overstabilization of charge transfer effects. Time-dependent density functional theory (TDDFT) using the B3LYP functional shows an analogous but less severe error for charge transfer states, whereas the ωB97 results are in good agreement with ADC(3). Multireference configuration interaction computations, which are in reasonable agreement with ADC(3), reveal that static correlation does not play a significant role. In the case of the larger Ir(ppy)3 complex, results at the TDDFT/B3LYP and TDDFT/ωB97 levels of theory are presented. Strong discrepancies between the two functionals, which are found with respect to the energies, characters, as well as the density of the low lying states, are discussed in detail and compared to experiment.

BACKGROUND

A simple rule based on short-acting inhaled β2-agonist (SABA) use could identify patients with chronic obstructive pulmonary disease (COPD) at increased risk of exacerbations and signal the need for maintenance therapy change, similar to asthma "Rules of Two(®)".

METHODS

Associations between SABA use, COPD exacerbations, and health care costs over 1 year were examined retrospectively using de-identified patient data from the Optum Research Database (ORD; N = 56,581) and the Impact National Benchmark Database (IMPACT™; N = 9423). Nebulized and metered-dose inhaler (MDI) SABA doses were normalized to 2.5 mg and 90 mcg albuterol equivalents, respectively.

RESULTS

The GOLD initiative establishes ≥2 exacerbations/year as indicative of increased risk in COPD. We identified a correlation (p < 0.0001) between 1.5 SABA doses/day and this frequency of exacerbations. In ORD, patients using ≥1.5 versus <1.5 SABA doses/day experienced significantly more exacerbations: 1.92 (95% confidence interval [CI], 1.89-1.96) versus 1.36 (95% CI, 1.34-1.38) per patient year (PPY). Above-threshold use was associated with higher average annual COPD-related costs (2010 $US): $21,868 (standard deviation [SD], $53,910) versus $11,686 (SD, $32,707) for nebulized SABA only, $9216 (SD, $30,710) versus $7334 (SD, $24,853) for MDI SABA only, and $15,806 (SD, $35,260) versus $11,233 (SD, $27,006) for both nebulized and MDI SABA. IMPACT™ validated these findings.

CONCLUSIONS

Patients with COPD using ≥1.5 SABA doses/day were at increased risk of exacerbations. Our results suggest a "Rule of 3-2": SABA use ≥3 times in 2 days should be considered a clinical marker for needing treatment reevaluation.

Polypyrrole (PPY) and poly-N-phenylpyrrole (PPPY) films were prepared and applied for solid-phase microextraction (SPME). The extraction properties of the new films to volatile organic compounds were examined using an SPME device coupled with GC-flame ionization detection. A PPY-coated capillary was applied for in-tube SPME to evaluate its extraction efficiency towards less volatile compounds and ionic species. The porous surface structures of the films, revealed by scanning electron microscopy, provided high surface areas and allowed for high extraction efficiency. Compared with commercial SPME stationary phases, the new phases showed better selectivity and sensitivity toward polar, aromatic, basic and anionic compounds, due to their inherent multifunctional properties. In addition, PPY and PPPY films showed different selectivity to various groups of compounds studied, indicating that the selectivity of the films could be modified by introducing a new functional group (phenyl in PPPY) into the polymer. For in-tube SPME, the PPY-coated capillary showed superior extraction efficiency to commercial capillaries for a variety of compounds, demonstrating its potential applications for a wide range of analytes when coupled with HPLC. The sensitivity and selectivity of the films for SPME could be tuned by changing the film thickness. These results are in line with both the theoretical expectations and the results obtained by other methods, which indicate not only that PPY films can be used as new stationary phases for SPME. but also that SPME method may provide an alternative tool for studying materials like polypyrrole.

Here we present the fabrication of polypyrrole (PPy) surfaces with a controlled overhang structure. Regularly structured PPy films were produced using interfacial polymerization around a sacrificial crystalline colloidal monolayer at the air/water interface. The morphology of the final inverse colloidal PPy film is controlled by the amount of monomer, the monomer: oxidant ratio and polymerization time. The PPy films exhibit an overhang structure due to depth of particle immersion in the water phase. As a result of the overhang structure, the PPy films are made hydrophobic, although the material itself is hydrophilic. The apparent contact angle of water on the structured surfaces is 109.5°, which is in agreement with the predicted contact angle using the Cassie-Baxter equation for air-filled cavities. This fabrication technique is scalable and can be readily extended to other systems where controlled wettability is required.

Mitochondrial morphology is important for the function of this critical organelle and, accordingly, altered mitochondrial structure is exhibited in many pathologies. Imaging of mitochondria can therefore provide important information about disease presence and progression. However, mitochondrial imaging is currently limited by the availability of agents that have the capacity to image mitochondrial morphology in both live and fixed samples. This can be particularly problematic in clinical studies or large, multi-centre cohort studies, where tissue archiving by fixation is often more practical. We previously reported the synthesis of an iridium coordination complex [Ir(ppy)2(MeTzPyPhCN)]+; where ppy is a cyclometalated 2-phenylpyridine and TzPyPhCN is the 5-(5-(4-cyanophen-1-yl)pyrid-2-yl)tetrazolate ligand; and showed that this complex (herein referred to as IraZolve-Mito) has a high specificity for mitochondria in live cells. Here we demonstrate that IraZolve-Mito can also effectively stain mitochondria in both live and fixed tissue samples. The staining protocol proposed is versatile, providing a universal procedure for cell biologists and pathologists to visualise mitochondria.

Electrical stimulation (ES) is widely applied to promote nerve regeneration. Currently, metal needles are used to exert external ES, which may cause pain and risk of infection. In this work, a multiblock conductive nerve scaffold with self-powered ES by the consumption of glucose and oxygen is prepared. The conductive substrate is prepared by in situ polymerization of polypyrrole (PPy) on the nanofibers of bacterial cellulose (BC). Platinum nanoparticles are electrodeposited on the anode side for glucose oxidation, while nitrogen-doped carbon nanotubes (N-CNTs) are loaded on the cathode side for oxygen reduction. The scaffold shows good mechanical property, flexibility and conductivity. The scaffold can form a potential difference of above 300 mV between the anode and the cathode in PBS with 5 × 10^-3 m glucose. Dorsal root ganglions cultured on the Pt-BC/PPy-N-CNTs scaffold are 55% longer in mean neurite length than those cultured on BC/PPy. In addition, in vivo study indicates that the Pt-BC/PPy-N-CNTs scaffold promotes nerve regeneration compared with the BC/PPy group. This paper presents a novel design of a nerve scaffold with self-powered ES. In the future, it can be combined with other features to promote nerve regeneration.

A nanocomposite comprising of polypyrrole and reduced graphene oxide was electrodeposited onto a carbon bundle fibre (CBF) through a two-step approach (CBF/PPy-rGO-2). The CBF/PPy-rGO-2 had a highly porous structure compared to a nanocomposite of polypyrrole and reduced graphene oxide that was electrodeposited onto a CBF in a one-step approach (CBF/PPy-rGO), as observed through a field emission scanning electron microscope. An X-ray photoelectron spectroscopic analysis revealed the presence of hydrogen bond between the oxide functional groups of rGO and the amine groups of PPy in PPy-rGO-2 nanocomposite. The fabricated CBF/PPy-rGO-2 nanocomposite material was used as an electrode material in a symmetrical solid-state supercapacitor, and the device yielded a specific capacitance, energy density and power density of 96.16 F g- 1, 13.35 Wh kg- 1 and of 322.85 W kg- 1, respectively. Moreover, the CBF/PPy-rGO-2 showed the capacitance retention of 71% after 500 consecutive charge/discharge cycles at a current density of 1 A g- 1. The existence of a high degree of porosity in CBF/PPy-rGO-2 significantly improved the conductivity and facilitated the ionic penetration. The CBF/PPy-rGO-2-based symmetrical solid-state supercapacitor device demonstrated outstanding pliability because the cyclic voltammetric curves remained the same upon bending at various angles. Carbon bundle fibre modified with porous polypyrrole/reduced graphene oxide nanocomposite for flexible miniature solid-state supercapacitor.

A simple and sensitive method for determining anatoxin-a in aqueous samples was developed using solid-phase microextraction (SPME) and gas chromatography with mass spectrometry (GC-MS) detection. Three forms of polyaniline (PANI) films and a single form of polypyrrole (PPY) film were prepared and applied for SPME. The extraction properties of these films to anatoxin-a were examined and it was shown that leucoemeraldine form of PANI displayed a better selectivity to this compound. SPME conditions were optimized by selecting the appropriate extraction parameters, including type of coating (leucoemeraldine form of PANI at 32 microm thicknesses), salt concentration (10%, w/v), time of extraction (30 min) and stirring rate (1000 rpm). The calibration curve was linear in the range from 50 to 10,000 ng/ml, with the detection limit (S/N = 3) of 11.2 ng/ml. This method was successfully applied for the analysis of anatoxin-a in the cultured media of two species of cyanobacteria.

A family of complexes (1a-3a and 1b-3b) was prepared, having the structure Ir(N^C^N)(N^C)Cl. Here, N^C(∧)N represents a terdentate, cyclometallating ligand derived from 1,3-di(2-pyridyl)benzene incorporating CH(3) (1a,b), F (2a,b), or CF(3) (3a,b) substituents at the 4 and 6 positions of the benzene ring, and N^C is 2-phenylpyridine (series a) or 2-(2,4-difluorophenyl)pyridine (series b). The complexes are formed using a stepwise procedure that relies on the initial introduction of the terdentate ligand to form a dichloro-bridged iridium dimer, followed by cleavage with the N^C ligand. (1)H NMR spectroscopy reveals that the isomer that is exclusively formed in each case is that in which the pyridyl ring of the N^C ligand is trans to the cyclometallating aryl ring of the N^C^N ligand. This conclusion is unequivocally confirmed by X-ray diffraction analysis for two of the complexes (1b and 3a). All of the complexes are highly luminescent in degassed solution at room temperature, emitting in the green (1a,b), blue-green (2a,b), and orange-red (3a,b) regions. The bidentate ligand offers independent fine-tuning of the emission energy: for each pair, the "b" complex is blue-shifted relative to the analogous "a" complex. These trends in the excited-state energies are rationalized in terms of the relative magnitudes of the effects of the substituents on the highest occupied and lowest unoccupied orbitals, convincingly supported by time-dependent density functional theory (TD-DFT) calculations. Luminescence quantum yields are high, up to 0.7 in solution and close to unity in a PMMA matrix for the green-emitting complexes. Organic light emitting devices (OLEDs) employing this family of complexes as phosphorescent emitters have been prepared. They display high efficiencies, at least comparable, and in some cases superior, to similar devices using the well-known tris-bidentate complexes such as fac-Ir(ppy)(3). The combination of terdentate and bidentate ligands is seen to offer a versatile approach to tuning of the photophysical properties of iridium-based emitters for such applications.

Carboxylic graphene oxide-composited polypyrrole/poly-l-lactic acid (C-GO/PPy/PLLA) films were fabricated by electrochemical deposition of C-GO-composited PPy on PLLA fibers-film, and their conductivity and tensile strength (∼4.6 S/cm and 26.4 MPa, respectively) were stably remained after the immersion of 4 weeks, due to the hydrogen bond interaction between graphene oxide's carboxylic groups and pyrrole's imino groups. Their specific surface areas of ∼57.5 m² /g and pore volume of ∼0.02 cm³ /g were significantly larger than those of PPy/PLLA films, due to the addition of C-GO nanosheets. Then, C-GO/PPy/PLLA conducting conduit with 2 mm inner diameter was prepared to bridge 10 mm sciatic nerve defect of rats, and the direction of fiber-axis in the conduit was the same as the conduit central axis. Electrical stimulation (ES) of 1 V and 20 Hz through the conducting conduit was exerted on the defect site. The results of in vivo electrophysiological and histological evaluation indicated that, the sciatic nerve defect could be repaired in C-GO/PPy/PLLA conduit, moreover the re-innervated gastrocnemius muscle and nerve conduction in C-GO/PPy/PLLA conduit & ES group were obviously better than the conduit without ES group. The results of transmission electron microscope analysis also demonstrated that the mean thickness of myelin sheath and diameter of axon in C-GO/PPy/PLLA conduit & ES group were significantly larger than those without ES, suggesting that the repair efficiency of ES & conduit group was closer to that of autograft group. These results indicated the great potential of C-GO/PPy/PLLA with the in vivo ES in the application of sciatic nerve repair.

A nitrogen-doped porous carbon material (N@MOG-C) was prepared by simple pyrolysis of polypyrrole-doped Al-based metal-organic gel (PPy@MOG) at 800 °C. The N@MOG-C possessed a uniform three-dimensional (3-D) interconnected mesoporous structure with a high surface area of 1542.6 m(2) g(-1) and a large pore volume of 0.76 cm(3) g(-1). By using an ionic liquid (IL) to immobilize N@MOG-C on electrode surface, the N@MOG-C was further used for sensitive detection of heavy metal ion. The doping of nitrogen-endowed N@MOG-C with faster electron transfer kinetics than other carbon materials such as MOG-C, multiwalled carbon nanotubes, and graphene. The N@MOG-C-modified electrode showed a high effective area, because of the porous structure. Under optimized conditions, the N@MOG-C-based sensor could detect Cd ions present in concentrations of 0.025-5 μM, with a detection limit of 2.2 nM. The mesoporous structure, fast electron transfer ability, and simple and green synthesis of N@MOG-C made it a promising electrode material for practical applications in heavy-metal-ion sensing.

Recent advances in super-resolution microscopy and fluorescence bioimaging allow exploring previously inaccessible biological processes. To this end, there is a need for novel fluorescent probes with specific features in size, photophysical properties, colloidal and optical stabilities, as well as biocompatibility and ability to evade the reticuloendothelial system. Herein, novel fluorescent nanoparticles are introduced based on an inherently fluorescent polypyrazoline (PPy) core and a polyethylene glycol (PEG) shell, which address all aforementioned challenges. Synthesis of the PPy-PEG amphiphilic block copolymer by phototriggered step-growth polymerization is investigated by NMR spectroscopy, size-exclusion chromatography, and mass spectrometry. The corresponding nanoparticles are characterized for their luminescent properties and hydrodynamic size in various aqueous environments (e.g., cell culture media). PPy nanoparticles particularly exhibit a large Stokes shift (Δλ = 160 nm or Δν>> 7000 cm-1 ) with visible light excitation and strong colloidal stability. While clearance by macrophages and endothelial cells is minimal, PPy displays good biocompatibility. Finally, PPy nanoparticles prove to be long circulating when injected in zebrafish embryos, as observed by in vivo time-lapse fluorescence microscopy. In summary, PPy nanoparticles are highly promising to be further developed as fluorescent nanodelivery systems with low toxicity and exquisite retention in the blood stream.

Coherence in the metal-metal-to-ligand-charge transfer (MMLCT) excited state of diplatinum molecule [Pt(ppy)(μ-(t)Bu(2)pz)](2) has been investigated through the observed oscillatory features and their corresponding frequencies as well as polarization dependence in the single-wavelength transient absorption (TA) anisotropy signals. Anticorrelated parallel and perpendicular TA signals with respect to the excitation polarization direction were captured, while minimal oscillatory features were observed in the magic angle TA signal. The combined analysis of the experimental results coupled with those previous calculated in the literature maps out a plausible excited state trajectory on the potential energy surface, suggesting that (1) the two energetically close MMLCT excited states due to the symmetry of the molecule may be electronically and coherently coupled with the charge density shifting back and forth between the two phenylpyridine (ppy) ligands, (2) the electronic coupling strength in the (1)MMLCT and (3)MMLCT states may be extracted from the oscillation frequencies of the TA signals to be 160 and 55 cm(-1), respectively, (3) a stepwise intersystem crossing cascades follows (1)MMLCT → (3)MMLCT (T(1b)) → (3)MMLCT (T(1a)), and (4) a possible electronic coherence can be modulated via the Pt-Pt σ-interactions over a picosecond and survive the first step of intersystem crossing. Future experiments are in progress to further investigate the origin of the oscillatory features. These experimental observations may have general implications in design of multimetal center complexes for photoactivated reactions where coherence in the excited states may facilitate directional charge or energy transfer along a certain direction between different parts of a molecule.