A novel cable-type flexible supercapacitor with excellent performance is fabricated using 3D polypyrrole(PPy)-MnO2 -CNT-cotton thread multi-grade nanostructure-based electrodes. The multiple supercapacitors with a high areal capacitance 1.49 F cm(-2) at a scan rate of 1 mV s(-1) connected in series and in parallel can successfully drive a LED segment display. Such an excellent performance is attributed to the cumulative effect of conducting single-walled carbon nanotubes on cotton thread, active mesoporous flower-like MnO2 nanoplates, and PPy conductive wrapping layer improving the conductivity, and acting as pseudocapacitance material simultaneously.

Improvement of cellular uptake and subcellular resolution remains a major obstacle in the successful and broad application of cellular optical probes. In this context, we design and synthesize seven non-emissive cyclometalated iridium(III) solvent complexes [Ir(CˆN)(2)(solv)(2)](+)L(-) (LIr2-LIr8, in which CˆN = 2-phenylpyridine (ppy) or its derivative; solv = DMSO, H(2)O or CH(3)CN; L(-) = PF(6)(-) or OTf(-)) applicable in live cell imaging to facilitate selective visualization of cellular structures. Based on the above variations (including different counter ions, solvent ligands, and CˆN ligands), structure-activity relationship analyses reveal a number of clear correlations: (1) variations in counter anions and solvent ligands of iridium(III) complexes do not affect cellular imaging behavior, and (2) length of the side carbon chain in CˆN ligands has significant effects on cellular uptake and localization/accumulation of iridium complexes in living cells. Moreover, investigation of the uptake mechanism via low-temperature and metabolism inhibitor assays reveal that [Ir(4-Meppy)(2)(CH(3)CN)(2)](+)OTf(-) (LIr5) with 2-phenylpyridine derivative with side-chain of methyl group at the 4-position as CˆN ligand permeates the outer and nuclear membranes of living cells through an energy-dependent, non-endocytic entry pathway, and translocation of the complex from the cell periphery towards the perinuclear region possibly occurs through a microtubule-dependent transport pathway. Nuclear pore complexes (NPCs) appear to selectively control the transport of iridium(III) complexes between the cytoplasm and nucleus. A generalization of trends in behavior and structure-activity relationships is presented, which should provide further insights into the design and optimization of future probes.

The design of complex heterostructured electrode materials that deliver superior electrochemical performances to their individual counterparts has stimulated intensive research on configuring supercapacitors with high energy and power densities. Herein we fabricate hierarchical tectorum-like α-Fe2 O3 /polypyrrole (PPy) nanoarrays (T-Fe2 O3 /PPy NAs). The 3D, and interconnected T-Fe2 O3 /PPy NAs are successfully grown on conductive carbon cloth through an easy self-sacrificing template and in situ vapor-phase polymerization route under mild conditions. The electrode made of the T-Fe2 O3 /PPy NAs exhibits a high areal capacitance of 382.4 mF cm-2 at a current density of 0.5 mA cm-2 and excellent reversibility. The solid-state asymmetric supercapacitor consisting of T-Fe2 O3 /PPy NAs and MnO2 electrodes achieves a high energy density of 0.22 mWh cm-3 at a power density of 165.6 mW cm-3 .

Six luminescent cyclometalated iridium(III)-dipyridoquinoxaline and -dipyridophenazine complexes [Ir(ppy)2(N-N)](PF6) (Hppy = 2-phenylpyridine; N-N = dipyrido[3,2-f:2',3'-h]quinoxaline, dpq (1); 2-n-butylamidodipyrido[3,2-f:2',3'-h]quinoxaline, dpqa (2); 2-((2-biotinamido)ethyl)amidodipyrido[3,2-f:2',3'-h]quinoxaline, dpqB (3); dipyrido[3,2-a:2',3'-c]phenazine, dppz (4); benzo[i]dipyrido[3,2-a:2',3'-c]phenazine, dppn (5); 11-((2-biotinamido)ethyl)amidodipyrido[3,2-a:2',3'-c]phenazine, dppzB (6)) have been designed as luminescent intercalators for DNA and probes for avidin. The structure of complex 4 has been studied by X-ray crystallography. The photophysical and electrochemical properties of the complexes have also been investigated. The binding of these complexes to double-stranded calf thymus DNA and synthetic double-stranded oligonucleotides poly(dA) x poly(dT) and poly(dG) x poly(dC) has been investigated by spectroscopic titrations. The interactions between the two biotin-containing complexes and avidin have been studied by 4'-hydroxyazobenzene-2-carboxylic acid (HABA) assays and emission titrations.

Bacterial infection has caused a serious threat to human public health. Methicillin-resistant Staphylococcus aureus (MRSA) is a representative drug-resistant bacterium, which is difficult to eradicate completely, resulting in high infection probability with severe mortality. Herein, pathogen-targeting phototheranostic nanoparticles, Van-OA@PPy, are developed for efficient elimination of MRSA infection. Van-OA@PPy nanoparticles are fabricated from the in situ templated formation of polypyrrole (PPy) in the presence of ferric ions (Fe3+) and a polymer template, hydrophilic poly(2-hydroxyethyl methacrylate-co-N,N-dimethyl acrylamide), P(HEMA-co-DMA). PPy nanoparticles are further coated with vancomycin conjugated oleic acid (Van-OA) to afford the resultant pathogen-targeting Van-OA@PPy. A high photothermal conversion efficiency of ∼49.4% is achieved. MRSA can be efficiently killed due to sufficient nanoparticle adhesion and fusion with MRSA, followed by photothermal therapy upon irradiation with an 808 nm laser. Remarkable membrane damage of MRSA is observed, which contributes greatly to the inhibition of MRSA infection. Furthermore, the nanoparticles have high stability and good biocompatibility without causing any detectable side effects. On the other hand, residual Fe3+ and PPy moieties in Van-OA@PPy endow the nanoparticles with magnetic resonance (MR) imaging and photoacoustic (PA) imaging potency, respectively. The current strategy has the potential to inspire further advances in precise diagnosis and efficient elimination of MRSA infection in biomedicine.

A new phosphorescent material of cyclometalated alkynylgold(III) complex, [Au(2,5-F(2)C(6)H(3)-C∧N∧C)(C≡C-C(6)H(4)N(C(6)H(5))(2)-p)] (1) (2,5-F(2)C(6)H(3)-HC∧N∧CH = 2,6-diphenyl-4-(2,5-difluorophenyl)pyridine), has been synthesized, characterized, and its device performance investigated. This luminescent gold(III) complex was found to exhibit rich PL and EL properties and has been utilized as phosphorescent dopants of OLEDs. At an optimized dopant concentration of 4%, a device with a maximum external quantum efficiency (EQE) of 11.5%, corresponding to a current efficiency of 37.4 cd/A and a power efficiency of 26.2 lm/W, has been obtained. Such a high EQE is comparable to that of Ir(ppy)(3)-based devices. The present work suggests that the alkynylgold(III) complex is a promising phosphorescent material in terms of both efficiency and thermal stability, with the additional advantages of its relatively inexpensive cost and low toxicity.

Herein graphene quantum dot (GQD), a graphene material with lateral dimension less than 100 nm, is explored to dope PPy on F-doped tin oxide glass as an efficient counter electrode for high-performance dye-sensitized solar cells (DSSCs). The GQDs-doped PPy film has a porous structure in comparison to the densely structured plain PPy, and displays higher catalytic current density and lower charge transfer resistance than the latter toward I3(-)/I(-) redox reaction. The highest power conversion efficiency (5.27%) for DSSCs is achieved with PPy doped with10% GQDs, which is comparable to that of Pt counter electrode-based DSSCs. This work provides an inexpensive alternative to replace platinum for DSSCs.

Bone implant materials cause the most common complication of bone infections in orthopedic surgery, resulting in implant failure. Antibiotic treatment of bone infections leads to problems such as bacterial resistance and reduced osteogenic capacity. In this study, dopamine (DA) was self-polymerized on the surface of Polylactic acid (PLLA)/Hydroxyapatite (HA) nanowire composite fibers to form an adhesive polydopamine (PDA) membrane, and a stable silver-nanoparticles (Ag-NPs) coating layer was constructed on it by electrochemically driven Ag⁺ coordination and chelation through Polypyrrole (PPy) mediation, achieving steady and slow release of Ag-NPs. With optimized DA soaking time of 24 h and soaking concentration of 0.5 g·L^-1, nanoparticles were uniformly distributed on PLLA/HA/PDA/PPy/Ag composite fibers and the hydrophilicity of the composite fibers was well-behaved. Besides, the composite fibers possessed good physiological stability and 100% antibacterial rate against Escherichia coli (E. coli) as well as Staphylococcus aureus (S. aureus). In addition, the composite fibers had promoted apatite nucleation and growth on surface and good cytocompatibility with osteoblasts, indicating ability of inducing osteogenic differentiation. In summary, a multi-functional PLLA/HA/PDA/PPy/Ag composite fiber with long-term antibacterial property, bioactivity and osteoinductivity was successfully constructed by electrospinning and electrochemical deposition.

We report a new method to promote the conductivities of metal-organic frameworks (MOFs) by 5 to 7 magnitudes, thus their potential in electrochemical applications can be fully revealed. This method combines the polarity and porosity advantages of MOFs with the conductive feature of conductive polymers, in this case, polypyrrole (ppy), to construct ppy-MOF compartments for the confinement of sulfur in Li-S batteries. The performances of these ppy-S-in-MOF electrodes exceed those of their MOF and ppy counterparts, especially at high charge-discharge rates. For the first time, the critical role of ion diffusion to the high rate performance was elucidated by comparing ppy-MOF compartments with different pore geometries. The ppy-S-in-PCN-224 electrode with cross-linked pores and tunnels stood out, with a high capacity of 670 and 440 mAh g-1 at 10.0 C after 200 and 1000 cycles, respectively, representing a new benchmark for long-cycle performance at high rate in Li-S batteries.

A novel 3-dimensional single wall carbon nanotubes (SWNTs)-polypyrrole (Ppy) composite was prepared as an electrode by chemically polymerizing polypyrrole onto SWNTs using a LiClO(4) oxidant. This composite electrode was characterized by scanning electron microscopy (SEM) and cyclic voltammetry with 1 mM [Fe(CN)(6)](-3)/[Fe(CN)(6)](-4). The SWNTs were thickly coated with chemically polymerized polypyrrole and the composite had many surface pores and crevices which could enhance mass transfer. The SWNTs-Ppy composite electrode showed a large specific surface area (30 m(2)/g) and a good reproducible current response, at about 100 times the peak current of a glassy carbon electrode (GCE). The diffusion coefficient was calculated to be 4.81x10(-6) cm(2)/s. As a biosensor application, tyrosinase was immobilized on the functionalized SWNTs and tyrosinase-SWNTs-Ppy composite was prepared in the same manner. This tyrosinase-SWNT-Ppy composite electrode was used for amperometric detection of dopamine in the presence of ascorbic acid and showed high sensitivity (467 mA/M cm(2)) and lower detection limit (5 microM) compared to previous reports.

With an excellent near-infrared (NIR) light-responsive property, polypyrrole (PPy) nanoparticle has emerged as a promising NIR photothermal transducing agent for tumor photothermal therapy (PTT). Herein, we reported the PVP mediated one-pot synthesis of colloidal stable and biocompatible PPy nanoparticles (PPy-PVP NPs) for combined tumor photothermal-chemotherapy. The influence of molecular weight and PVP concentration on the spectroscopic characteristic, photothermal feature, drug loading performance, and antitumor efficiency of the resultant PPy-PVP NPs was systematically studied. By choosing PVP with a molecular weight of 360 kDa (concentration of 5 mg/mL) as the template and surface modifier during the synthesis, PPy-PVP NPs with optimal spectroscopic characteristic, photothermal feature, drug loading performance, and antitumor efficiency were synthesized. Findings in this study are anticipated to provide an in-depth understanding of the important character of surface engineering in the rational design and biomedical applications of PPy NPs.

Mimicking soft tissue mechanical properties and the high conductivity required for electrical transmission in the native spinal cord is critical in nerve tissue regeneration scaffold designs. However, fabricating scaffolds of high conductivity, tissue-like mechanical properties, and excellent biocompatibility simultaneously remains a great challenge. Here, a soft, highly conductive, biocompatible conducting polymer hydrogel (CPH) based on a plant-derived polyphenol, tannic acid (TA), cross-linking and doping conducting polypyrrole (PPy) chains is developed to explore its therapeutic efficacy after a spinal cord injury (SCI). The developed hydrogels exhibit an excellent electronic conductivity (0.05-0.18 S/cm) and appropriate mechanical properties (0.3-2.2 kPa), which can be achieved by controlling TA concentration. In vitro, a CPH with a higher conductivity accelerated the differentiation of neural stem cells (NSCs) into neurons while suppressing the development of astrocytes. In vivo, with relatively high conductivity, the CPH can activate endogenous NSC neurogenesis in the lesion area, resulting in significant recovery of locomotor function. Overall, our findings evidence that the CPHs without being combined with any other therapeutic agents have stimulated tissue repair following an SCI and thus have important implications for future biomaterial designs for SCI therapy.

Highly porous polypyrrole (PPy)-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg(-1), were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30-50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m(2) g(-1)) of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT)(6), (dT)(20), and (dT)(40) DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules.

Redox enzyme - glucose oxidase E.C. 1.1.3.4 from Penecillum vitale (GOx) - initiated polypyrrole (Ppy) synthesis was applied for the formation of polypyrrole based nanoparticles. The increase in optical absorbance at lambda=460 nm was exploited for the monitoring of polypyrrole polymerisation process. The shape and size of the formed Ppy nanoparticles was also monitored by means of contact mode AFM. The highest increase in the diameter of the formed Ppy nanoparticles was detected during 15-day period. AFM imaging was performed in contact mode to investigate the shape and flexibility of particles deposited on the SiO2 and Pt surfaces. Contact mode AFM investigations allowed us to conclude that after drying at 50 degrees C the formed Ppy particles are more flexibly deposited on the Pt electrode if compared to those deposited on the SiO2 substrate. The application of well-shaped Ppy nanoparticles in biomedicine, chromatography and bioanalysis may be predicted.

There is a global debate and concern about the use of glyphosate (Gly) as an herbicide. New toxicological studies will determine its use in the future under new strict conditions or its replacement by alternative synthetic or natural herbicides. In this context, we designed biomimetic polymer sensing layers for the selective molecular recognition of Gly. Towards this end, complementary surface acoustic wave (SAW) and electrochemical sensors were functionalized with polypyrrole (PPy)-imprinted polymer for the selective detection of Gly. Their corresponding limits of detection were on the order of 1 pM, which are among the lowest values ever reported in literature. The relevant dissociation constants between PPy and Gly were estimated at [Kd1 = (0.7 ± 0.3) pM and Kd2 = (1.6 ± 1.4) µM] and [Kd1 = (2.4 ± 0.9) pM and Kd2 = (0.3 ± 0.1) µM] for electrochemical and gravimetric measurements, respectively. Quantum chemical calculations permitted to estimate the interaction energy between Gly and PPy film: ΔE = -145 kJ/mol. Selectivity and competitivity tests were investigated with the most common pesticides. This work conclusively shows that gravimetric and electrochemical results indicate that both MIP-based sensors are perfectly able to detect and distinguish glyphosate without any ambiguity.

We report a rapid-response and high-sensitivity sensor with specificity toward H2O2 based on a liquid-ion-gated field-effect transistor (FET) using graphene-polypyrrole (PPy) nanotube (NT) composites as the conductive channel. The rGO, PPy, NTs, and nanocomposite materials were characterized using Raman spectroscopy, Fourier transform-infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). On the basis of these results, a well-organized structure is successfully prepared owing to the specific interactions between the PPy NTs and the rGO sheet. Reliable electrical contacts were developed between the rGO/PPy NTs and the microelectrodes, which remained stable when exposed to the liquid-phase analyte. Liquid-ion-gated FETs composed of these graphene nanocomposites exhibited hole-transport behavior with conductivities higher than those of rGO sheets or PPy NTs. This implies an interaction between the PPy NTs and the rGO layers, which is explained in terms of the PPy NTs forming a bridge between the rGO layers. The FET sensor provided a rapid response in real time and high sensitivity toward H2O2 with a limit of detection of 100 pM. The FET-type biosensing geometry was also highly reproducible and stable in air. Furthermore, the liquid-gated FET-type sensor exhibited specificity toward H2O2 in a mixed solution containing compounds found in biological fluids.

Multifunctional supramolecular nanomaterials capable of targeted and multimodal therapy hold great potential to improve the efficiency of cancer therapeutics. Herein, we report a proof-of-concept nanoplatform for effective chemophotothermal therapy via the integration of folic acid-based active targeting and supramolecular nanovalves-based passive targeting. Inspired by facile surface engineering and designable layer-by-layer assembly concept, we design and synthesize PPy@UiO-66@WP6@PEI-Fa nanoparticles (PUWPFa NPs) to achieve efficient synergistic chemophotothermal therapy, taking advantage of the desirable photothermal conversion capability of polypyrrole nanoparticles (PPy NPs) and high drug-loading capacity of hybrid scaffolds. Significantly, pillararene-based pseudorotaxanes as pH/temperature dual-responsive nanovalves allow targeted drug delivery in pathological environment with sustained release over 4 days, which is complementary to photothermal therapy, and folic acid-conjugated polyethyleneimine (PEI-Fa) at the outmost layer through electrostatic interactions is able to enhance tumor-targeting and therapeutic efficiency. Such PUWPFa NPs showed efficient synergistic chemophotothermal therapy of cervical cancer both in vitro and in vivo. The present strategy offers not only the distinctly targeted drug delivery and release, but also excellent tumor inhibition efficacy of simultaneous chemophotothermal therapy, opening a new avenue for effective cancer treatment.

A bienzymatic glucose biosensor was proposed for selective and sensitive detection of glucose. This mediatorless biosensor was made by simultaneous immobilization of glucose oxidase (GOD) and horseradish peroxidase (HRP) in an electropolymerized pyrrole (PPy) film on a single-wall carbon nanotubes (SWNT) coated electrode. The amperometric detection of glucose was assayed by potentiostating the bienzymatic electrode at -0.1 versus Ag/AgCl to reduce the enzymatically produced H(2)O(2) with minimal interference from the coexisting electroactive compounds. The single-wall carbon nanotubes, sandwiched between the enzyme loading polypyrrole (PPy) layer and the conducting substrate (gold electrode), could efficiently promote the direct electron transfer of HRP. Operational characteristics of the bienzymatic sensor, in terms of linear range, detection limit, sensitivity, selectivity and stability, were presented in detail.

The novel steroidal conjugate 17-α-[2-phenylpyridyl-4-ethynyl]-19-nortestosterone (LEV-ppy) (1) and the steroid-C,N-chelate ruthenium(II) conjugate [Ru(η(6)-p-cymene)(LEV-ppy)Cl] (2) have been prepared. At 48 h incubation time, complex 2 is more active than cisplatin (about 8-fold) in T47D (breast cancer) and also shows an improved efficiency when compared to its nonsteroidal analogue [Ru(η(6)-p-cymene)(ppy)Cl] (ppy = phenylpyridine) (3) in the same cell line. The act of conjugating a levonorgestrel group to a ruthenium(II) complex resulted in synergistic effects between the metallic center and the steroidal ligand, creating highly potent ruthenium(II) complexes from the inactive components. The interaction of 2 with DNA was followed by electrophoretic mobility. Theoretical density functional theory calculations on complex 2 show the metal center far away from the lipophilic steroidal moiety and a labile Ru-Cl bond that allows easy replacement of Cl by N-nucleophiles such as 9-EtG, thus forming a stronger Ru-N bond. We also found a minimum energy location for the chloride counteranion (4(+)·Cl(-)) inside the pseudocavity formed by the α side of the steroid moiety, the phenylpyridine chelating subsystem, and the guanine ligand, i.e., a host-guest species with a rich variety of nonbonding interactions that include nonclassical C-H···anion bonds, as supported by electrospray ionization mass spectra.

A highly useful, visible-light-driven carboxylation of aryl bromides and chlorides with CO2 was realized using a combination of Pd(OAc)2 as a carboxylation catalyst and Ir(ppy)2(dtbpy)(PF6) as a photoredox catalyst. This carboxylation reaction proceeded in high yields under 1 atm of CO2 with a variety of functionalized aryl bromides and chlorides without the necessity of using stoichiometric metallic reductants.

A novel electrochemical sensor using the molecularly imprinted (MIP) oxygen-containing polypyrrole (PPy) decorated carbon nanotubes (CNTs) composite was proposed for in vivo detection of dopamine (DA). The prepared sensor exhibits a remarkable sensitivity of (16.18μA/μM) with a linear range of 5.0×10(-11)-5.0×10(-6)M and limit of detection as low as 1.0×10(-11)M in the detection of DA, which might be due to the plenty cavities for binding DA through π-π stacking between aromatic rings and hydrogen bonds between amino groups of DA and oxygen-containing groups of the novel PPy.

A disposable glucose biosensor based on glucose oxidase immobilized on tetrathiafulvalene-tetracyanoquinodimethane (ITF-TCNQ) conducting organic salt synthesized in situ onto an overoxidized poly(pyrrole) (PPy(ox).) film is described. The TIF-TCNQ crystals grow through the nonconducting polypyrrole film (ensuring electrical connection to the underlying Pt electrode) and emerge from the film forming a treelike structure. The PPy(ox) film prevents the interfering substances from reaching the electrode surface. The sensor behavior can be modeled by assuming a direct reoxidation of the enzyme at the surface of the TTF-TCNQ crystals. A heterogeneous rate constant around 10(-6) - 10(-7) cm s(-1) has been estimated. The biosensor is nearly oxygen- and interference-free and when integrated in a flow injection system displays a remarkable sensitivity (70 nA/mM) and stability.

The novel steroidal conjugates [M(η(5)-C(5)Me(5))Cl(LEV-ppy)] (M = Rh (1) and Ir (2)) bearing the lipophilic levonorgestrel group 17-α-[2-phenylpyridyl-4-ethynyl]-19-nortestosterone (LEV-ppy), where the chelating ligand is N and C-bound, have been prepared and characterized. Both compounds are more active than cisplatin (about 6-fold) in T47D (breast cancer) at 48 h incubation time. On the other hand, very low resistance factors (RF) of 1 and 2 in A2780cisR (cisplatin-resistant ovarian carcinoma) at 48 h were observed (RF = 0.9 and 1.1, respectively). The iridium steroidal compound 2 is twice as active as the non-steroidal analogue 2', whose promising anticancer activity has recently been reported by Sadler. Theoretical DFT calculations on complexes 1 and 2 at the B3LYP-D/def2-TZVP-ecp level of theory show that the strongest bond to the metal atom is the η(5)-interaction to the Cp* ligand and that both of them feature a rather strong metal-chlorine bond. The new steroidal conjugates 1 and 2 are able to bind to DNA according to Hoechst 33258 displacement experiments and ESI-TOF MS spectrometry studies. Complexes 1 and 2 are also cathepsin B inhibitors, an enzyme implicated in a number of cancer related events.