Search

Repeated bilayers of a polycation and a polyanion were assembled by adsorption from their aqueous solutions. The polycations used were PEI (poly(ethylenimine)), PAH (poly(allylamine hydrochloride)), and generation 3.0 dendrimer (poly(propylenimine)). The polyanion was PAZO (poly[1-[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethanediyl, sodium salt]). Second harmonic generation (SHG) and UV−vis spectroscopy were used to study the structure and formation of the superlattices. The linear increase in absorbance versus the number of bilayers suggested that a uniform and consistent amount of polymer adsorbed during each deposition cycle. The observation of a second harmonic (SH) signal from the film showed that the conjugated chromophores in the PAZO polymer were aligned with a net dipole. However, the SHG signal did not continue to increase as the number of bilayers was increased. On the basis of thorough studies of the UV and SH properties for each bilayer for 10 total bilayers, we propose that t...

Polyaniline- emeraldine base (EB) fiber with excellent mechanical and electrical properties have been spun from highly concentrated (20% w/w), EB/N-methyl- 2-pyrrolidinone (NMP)/2-methylaziridine (2 MA) solution. These solutions had gelation times, which varied from hours to days depending on the molar ratio of 2 MA to EB tetramer repeating unit in the N-methyl-2-pyrrolidinone (NMP) solvent. To better compare the mechanical and electrical properties, dense films were also prepared by thermal evaporation of less concentrated solution (1% w/w). Both fibers and films were amenable to thermal stretching with maximum draw ratios o f4:1a ndthese stretched samples exhibited the greatest tensile strength overall. Wide-angle X-ray diffraction (WAXD) of as-spun and 4-times stretched fiber showed a completely amorphous struc- ture. Fiber subjected to heat treatment at 250 °C under N2 flux for 2 h displayed further improvements in mechanical properties because of crosslinking between the polymer chains. Fibers and films were later doped by immersion in a variety of aqueous acid solutions. Room temperature DC conductivities for the doped samples ranged from 6 3 10 24 to 45 S/cm depending on the specific choice of acid. Scanning electron micros- copy of fiber samples shows the presence of macrovoid formation during fiber spinning. Continued refinement of the processing parameters and fiber post-treatment, to en- hance chain alignment and increase fiber density, will likely lead to additional improve- ments in the fiber mechanical and electrical properties. Characterization of emeraldine base (EB) powder, solution, films, and fibers by UV-Vis, DSC, TGA, and WAXD were also performed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 194 -204, 2000

We report the synthesis and characterization of multi-layered organic superlattices made by polyelectrolyte self-assembly. Self-assembled films were formed from a water-soluble form of poly(phenylene vinylene) with high-photoluminescence quantum efficiency (QE). We observed a self-quenching of the luminescence with increasing film thickness. This quenching can be reversed by inserting spacer layers between each active conjugated layer. A red shift of the luminescence was also observed as additional poly(phenylene vinylene) layers were added. We attribute the red shift and increasing QE to changing polymer conformation, together with efficient unidirectional energy transfer. We rule out quantum confinement as the origin of the red shift.

The fluorescence of a polyanionic conjugated polymer can be quenched by extremely low concentrations of cationic electron acceptors in aqueous solutions. We report a greater than million-fold amplification of the sensitivity to fluorescence quenching compared with corresponding “molecular excited states.” Using a combination of steady-state and ultrafast spectroscopy, we have established that the dramatic quenching results from weak complex formation [polymer (−) /quencher (+) ], followed by ultrafast electron transfer from excitations on the entire polymer chain to the quencher, with a time constant of 650 fs. Because of the weak complex formation, the quenching can be selectively reversed by using a quencher-recognition diad. We have constructed such a diad and demonstrate that the fluorescence is fully recovered on binding between the recognition site and a specific analyte protein. In both solutions and thin films, this reversible fluorescence quenching provides the basis for a new class of highly sensitive biological and chemical sensors.

Charge-transfer polymers are a new class of nonlinear optical materials which can be used for generating femtosecond holographic gratings. Using semiconducting polymers sensitized with varying concentrations of C 60 , holographic gratings were recorded by individual ultrafast laser pulses; the diffraction efficiency and time decay of the gratings were measured using non-degenerate four-wave mixing. Using a figure of merit for dynamic data processing, the temporal diffraction efficiency, this new class of materials exhibits between two and 12 orders of magnitude higher response than any other class of material. The high quantum efficiency and metastability of the charge transfer enables tuning of the decay dynamics by controlling the concentration of acceptors in the blend.

Light-emitting electroluminescent diodes and electrochemically-driven electroluminescent devices involving conjugated polymers are described. The effect on the properties of polypyrrole films (deposited from aqueous polymerizing solutions of pyrrole) caused by the hydrophilicity/hydrophobicity of the substrate surface is utilized by a microcontact printing technique to form patterned liquid crystal display devices.

We report the fabrication of polymer grid triodes (PGTs) using C60 as the semiconducting medium. The structure, a self-assembling porous conducting polyaniline network placed between two semiconducting layers of C60, and sandwiched between two metal electrodes, demonstrates the I–V characteristics of a three terminal device in which the current is controlled by the grid potential. As a result of the higher mobilities of the fullerenes compared to those of conjugated polymers, the fullerene devices offer some performance advantages; the operating voltages are less than 5 V with current densities exceeding 1 mA/cm2. By fabricating devices with different grid densities, it is shown that the grid exhibits a strong influence on the I–V characteristics for high grid densities, and a correspondingly low influence for low densities, in agreement with theory. The I–V characteristics of the C60 PGTs are well described by an effective diode model, similar to that used for vacuum triodes.

The high molecular weight (M n > 30,000, M w >120,000) form of emeraldine base (EB) may be dissolved at concentrations exceeding 20% (w/w) in organic solvents for periods of time sufficient to dry-wet spin solid fibers. This result is due to the combination of a gel-inhibitor (GI) with the polymer/solvent solution. The GI/EB complex disrupts hydrogen bond formation between EB chains in the concentrated EB solutions and thereby lowers the solution viscosity and increases the gelation time. The as spun fiber exhibits good mechanical strength and high conductivities, and both physical properties are further improved by drawing the fiber to four times its initial length. Doping the fibers with inorganic mineral acids significantly reduces fiber strength, while doping with certain organic acids, such as benzene phosphinic acid, preserves mechanical properties and high conductivity values. All of the fully doped fibers show temperature activated conductivity. No detectable crystallinity was observed by measurements with a wide angle XRD technique.

We report a study of critical current density J/sub c/ as a function of temperature T, magnetic field H, and film thickness d in a series of high quality YBa/sub 2/Cu/sub 3/O/sub 7-/spl delta// (YBCO) films. A crossover in the thickness dependence of J/sub c/(H) curves was observed for T>50 K, where thinner film carries significantly lower J/sub c/(H) than thicker film at high fields, while the opposite was observed at low fields. This J/sub c/(H) crossover behavior seems to be a general feature for a superconducting system with a spectrum of pinning density, whose trend opposes to the effective volume faction for J/sub c/. This generalization is supported by examining J/sub c/(H) crossover behaviors observed earlier in the Bi/sub 2/Sr/sub 2/Ca/sub 2/Cu/sub 3/O/sub 10+/spl delta//(Bi2223)/Ag tapes irradiated with 5.8 GeV Pb ions, where enhanced J/sub c/(H) at high fields is attributed to the density increase in the columnar flux pinning centers.

Nitrogen-doped graphene/graphene-tube nanocomposites are prepared by a hightemperature approach using a newly designed cage-containing metal-organic framework (MOF) to template nitrogen/carbon (dicyandiamide) and iron precursors. The resulting N-Fe-MOF catalysts universally exhibit high oxygen-reduction activity in acidic, alkaline, and non-aqueous electrolytes and superior cathode performance in Li-O2 batteries.

Plasmon-driven chemical reaction of p-nitrothiophenol (pNTP) dimerizing into p,p′-dimercaptoazobenzene (DMAB) has been monitored using single particle surface enhanced Raman spectroscopy, which provides laser wavelength- and power-dependent conversion rates of the reaction.

A non-precious metal catalyst for oxygen reduction in acid media, enriched in graphene sheets/bubbles during a high-temperature synthesis step, has been developed from an Fe precursor and in situ polymerized polyaniline, supported on multi-walled carbon nanotubes. The catalyst showed no performance loss for 500 hours in a hydrogen/air fuel cell. The improved durability is correlated with the graphene formation, apparently enhanced in the presence of carbon nanotubes.

Symmetrically configured a.c. light-emitting (SCALE) ‘5-layer’ devices having the configuration M/EB/P/EB/ITO, where M = Al, Cu or Au, EB = polyaniline (emeraldine base), P = poly(2,5-dihexadecanoxy phenylene vinylene pyridyl vinylene) or PPV-PPyV, and ITO = indium-tin oxide glass, show electroluminescent properties in both forward and reverse bias modes. In the absence of emeraldine base, in the case of aluminum and copper, electroluminescence is observed only in the forward biasmode; in the case of gold no electroluminescence is observed in either forward or reverse bias modes. The electrical properties of the ‘5-layer’ devices (M = Al, Cu) are most surprising since their total resistance at a given applied voltage is significantly less than that of the corresponding devices in which the two polyaniline insulator layers are not present.

Photophysics and light-emitting device applications of poly ( p -pyridine) - and poly( p -pyridyl vinylene)-based polymers are presented. Extensive time-resolved (ps to ms) photoluminescence, stimulated emission and photoinduced absorption studies of solutions, powders and films demonstrate that the primary photoexcitation of these polymers is an intrachain singlet exciton. The presence of (n,π * ) states leads to enhanced intersystem crossing to triplet excitons for the powder form, while aggregate formation plays a key role in the films. Polarons are important at longer times. These polymers were used to fabricate ‘conventional’ polymer light-emitting diodes. In addition, these polymers were used to demonstrate a novel light-emitting structure, the symmetrically configured a.c. light-emitting (SCALE) device. These new devices have potential advantages in their use with high workfunction electrodes, such as gold, and also in their a.c. operation.

We report the fabrication of several multilayer light-emitting-diode (LED) devices based on a novel conjugated polymer, poly(2,5-dihexadecanoxy phenylene vinylene pyridyl vinylene) (PPV-PPy V), involving the use of polyaniline (emeraldine base, EB) as an insulating layer between the emissive polymer layer and the electrodes. In all the above devices with various configurations (‘3-layers’, ‘4-layers’-1’, ‘4-layers-2’ and ‘5-layers’), only the symmetrically configured a.c. light-emitting (SCALE) (‘5-layers’) device shows the capability of operating in both forward and reverse bias modes and in an a.c. mode. The SCALE devices have a typical turn-on voltage of about 4–6 V and work well under both forward and reverse bias modes. It is important to note that the total resistance ( R= V/I +) of the four devices at any given applied potential decreases as the number of insulating polymer layers increases, suggesting that the nature of the electrode/polymer interface plays a critical role in determining the characteristics of the devices.

Enhanced in-field critical current densities (Jc’s) have been obtained in epitaxial superconducting (RE1,RE2)Ba2Cu3O7−x (RE1=rare‐earthion 1, and RE2=rare earth ion 2) films grown on both single crystal and buffered metallic substrates. For a constant average RE ionic radius (equal to that of yttrium), there is a systematic dependence of the in-field Jc on the RE ion size variance, with a small, but nonzero, variance being optimum. Compared to the standard YBa2Cu3O7−x composition, a factor of two improvement in Jc(75.5K) is reproducibly observed at 0.2T(‖c) for the composition Dy1∕3Ho2∕3Ba2Cu3O7−x on both single crystal and buffered-metallic substrates. Angular dependent magnetic field studies and transmission electron microscopy indicate the presence of additional pointlike random defects.

Magnetron-sputter-deposited austenitic 330 stainless steel (330 SS) films, several microns thick, were found to have a hardness ∼6.5 GPa, about an order of magnitude higher than bulk 330 SS. High-resolution transmission electron microscopy revealed that sputtered 330 SS coatings are heavily twinned on {111} with nanometer scale twin spacing. Molecular dynamics simulations show that, in the nanometer regime where plasticity is controlled by the motion of single rather than pile-ups of dislocations, twin boundaries are very strong obstacles to slip. These observations provide a new perspective to producing ultrahigh strength monolithic metals by utilizing growth twins with nanometer-scale spacing.

Here we demonstrate, for the first time, the fabrication of Au nanostructures on polyaniline (PANI) membrane surfaces for surface enhanced Raman spectroscopy (SERS) applications, through a direct chemical reduction by PANI. Introduction of acids into the HAuCl(4) solution leads to homogeneous Au structures on the PANI surfaces, which show only sub-ppm detection levels toward the target analyte, 4-mercaptobenzoic acid (4-MBA), because of limited surface area and lack of surface roughness. Thorny Au nanostructures can be obtained through controlled reaction conditions and the addition of a capping agent poly (vinyl pyrrolidone) (PVP) in the HAuCl(4) solution and the temperature kept at 80 °C in an oven. Those thorny Au nanostructures, with higher surface areas and unique geometric feature, show a SERS detection sensitivity of 1 × 10(-9) M (sub-ppb level) toward two different analyte molecules, 4-MBA and Rhodamine B, demonstrating their generality for SERS applications. These highly sensitive SERS-active substrates offer novel robust structures for trace detection of chemical and biological analytes.

We demonstrate that photon antibunching observed for individual nanocrystal quantum dots (NQDs) can be transformed into photon bunching characterized by super-Poissonian statistics when they are coupled to metal nanostructures (MNs). This observation indicates that, while the quantum yield of a biexciton (${Q}_{2\mathrm{X}}$) is lower than that of a single exciton (${Q}_{1\mathrm{X}}$) in freestanding NQDs, ${Q}_{2\mathrm{X}}$ becomes greater than ${Q}_{1\mathrm{X}}$ in NQDs coupled to MNs. This unique phenomenon is attributed to metal-induced quenching with a rate that scales more slowly with exciton multiplicity than the radiative decay rate and dominates over other nonradiative decay channels for both single excitons and biexcitons.

Tradition graphene anodes in lithium ion batteries (LIBs) suffer significant performance loss due to the restacking of graphene layers. In this work, we have demonstrated a facile synthesis of preparing a series of graphene-derived nanomaterials. Among other potential application, these nanomaterials achieved an excellent cyclic durability with much enhanced capacity as novel anode materials in LIBs. These exceptional metrics observed within the novel assemblies is primarily due to the robust structure along with the optimal d-spacing allowing for facilitated Li adsorption/desorption and diffusion. Furthermore, the significantly enhanced rate performance was achieved after optimizing the structure of the self-assemblies. Development of nanomaterials anode suggests that the optimal design of graphene materials with robust structures is very important for next generation LIBs with high-energy storage efficiencies.

We report on the structural and transport properties of EuBa2Cu3O7−x (Eu123) films on SrTiO3 substrates. A substrate temperature 100 °C higher than that used to deposit YBa2Cu3O7−x (Y123) is needed to grow high-performance Eu123 films directly on SrTiO3 substrates. However, this high-temperature restriction can be circumvented by inserting a seed layer (∼12 nm) of Y123, Gd123, or Dy123 between the substrate and the Eu123. A structural analysis reveals that a transition region that promotes the growth of the a-axis is first formed on the surface of the substrate if the Eu123 is deposited directly on SrTiO3 at a temperature of less than 800 °C. On the other hand, the use of a seed layer of another superconducting material restructures the Eu123 to the right phase without forming this transition region. Eu123 films with critical temperatures of 94 K and critical current densities of 5.8×106 A/cm2 at 75.5 K have been deposited under standard deposition conditions using such an approach.

One of the most intensely researched subjects in the development of YBa2Cu3O7−δ (YBCO)-based coated conductors is the methodology for achieving ever-sharper film texture on flexible metal substrates. This is a critical issue due to the intrinsic weak-link behavior that results in depressed critical current density (Jc) in polycrystalline YBCO. Using ion-beam-assisted deposition of magnesium oxide, we have achieved YBCO texture on superalloy substrates approaching that on single-crystal oxide substrates. This advance has allowed us to fabricate coated conductor samples with Jcs that are as high as for films on oxide crystals; for example, >2 MA/cm2 (75 K, self-field) at a YBCO thickness of ∼1.5 μm.

Imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, and benzimidazole were subjected to electrochemical and chemical oxidation. Chemical oxidation yields oligomers with higher molecular weight (DP>12) than anodic oxidation (DP>6) as detected by laser desorption mass spectrometry (LDMS). The oligomers have a relatively simple structure in which imidazole moieties are linked by N-N bonds. 1-Methylimidazole does not polymerize, and benzimidazole seems to react through the benzene carbon atoms as well as through the nitrogen atoms. Solubility of these products varies with the substituent group on the imidazole ring

A simple one-pot reaction using in situ chemically generated Na-naphthalenide as an electron reductant in the preferential generation of C602− is described. Trapping of C602− intermediate with 2 molar equiv of sterically hindered 2-bromo-2-methylmalonate ester afforded two singly bonded fullerenyl bisadducts C60[-CMe(CO2Et)2]2 in 35% and 7% yield, respectively. The regiochemistry of these two products was determined to be 1,4- and 1,16-bisadducts, respectively, by NMR, UV−vis−NIR, LCMS, and X-ray single crystal structural analysis. The minor 1,16-bisadduct 2 exhibits long wavelength absorption bands in the near-IR region and prominent electron-accepting characteristics as compared with those of the major 1,4-bisadduct and pristine C60. As revealed by DFT calculation, we propose that the origin of these unusual characters of 2 arises from the moiety of [18π]-trannulene, in close resemblance to that of the highly symmetrical emerald green 1,16,29,38,43,60-hexaadduct of C60, EF-6MCn. Accordingly, we anticipa...

A simple one-pot reaction using in situ chemically generated Na-naphthalenide as an electron reductant in the preferential generation of C(60)(2-) is described. Trapping of C(60)(2-) intermediate with 2 molar equiv of sterically hindered 2-bromo-2-methylmalonate ester afforded two singly bonded fullerenyl bisadducts C(60)[-CMe(CO(2)Et)(2)](2) in 35% and 7% yield, respectively. The regiochemistry of these two products was determined to be 1,4- and 1,16-bisadducts, respectively, by NMR, UV-vis-NIR, LCMS, and X-ray single crystal structural analysis. The minor 1,16-bisadduct 2 exhibits long wavelength absorption bands in the near-IR region and prominent electron-accepting characteristics as compared with those of the major 1,4-bisadduct and pristine C(60). As revealed by DFT calculation, we propose that the origin of these unusual characters of 2 arises from the moiety of [18pi]-trannulene, in close resemblance to that of the highly symmetrical emerald green 1,16,29,38,43,60-hexaadduct of C(60), EF-6MC(n). Accordingly, we anticipate a fast progressive formation of plausible 1,16-bisadduct-like intermediate moieties on a C(60) cage as the precursor structure leading to the formation of EF-6MC(n), by taking the corresponding regiochemistry and electronic properties into account.

Initial experiments using differentially functionalized fullerenes, CD- C 6 0 , hexa- C 6 0 , and tris- C 6 0 , suggested a properties dependent effect on cytotoxic and proliferative responses in human skin keratinocytes. In the present study we investigated the cytokine secretion profile of dermal epithelial cells exposed to functionalized fullerenes. Keratinocyte-derived cytokines affect homing and trafficking of normal and malignant epidermal immune as well as nonimmune cells in vivo. These cytokines are critical for regulating activation, proliferation, and differentiation of epidermal cells. Our results indicate that tris- C 6 0 (size range

Blends of polypyrrole (PPy) and poly(vinyl methyl ketone) (PVMK) have been prepared both chemically and electrochemically. Hydrogen bonding between PPy and PVMK has been verified by IR spectroscopy. No significant change in conductivity occurs on stretching the blends over 200%. PPy/PVMK blends prepared chemically and electrochemically exhibit threshold conductivities near 10% PPy. X-ray diffraction spectra suggest that crystallinity does not vary with PPy concentration in the blend. Conductivity vs temperature and conductivity vs moisture are reported as measures of environmental stability

We report reversible thermochromism of a conjugated polymer, poly{2,5-bis[3-(N,N-diethylamino)-1-oxapropyl]-1,4-phenylenevinylene} (DAO-PPV), in diluted solutions of toluene and 1,2-dichlorobenzene. By means of temperature- and solvent-dependent steady-state spectroscopy, picosecond time-resolved photoluminescence spectroscopy, and dynamic light scattering, we provide new insights into the role of polymer aggregates in defining the thermochromic behavior of PPVs. We find DAO-PPV to exhibit a low temperature state with vibronically structured red visible absorption and emission spectra. Structurally, this low temperature state is a densely packed and disordered polymer aggregate, which contains a fraction of well-ordered, packed polymer chains. These ordered regions serve as low energy trap sites for the more disordered regions in the aggregate, thus regulating the final emission of the aggregate and imposing a vibronically resolved emission spectrum, which is usually associated with emission from one or a few chromophores. The high temperature state of DAO-PPV is a loose aggregate, with structureless absorption and emission spectra in the green visible range. Structurally, the loose aggregate is a well-solvated aggregate retaining the physical dimension of the dense aggregate but for which interchain interactions are diminished with the increase of temperature. As a result, the spectroscopic behavior of the loose aggregate is very similar if not identical to that of the single polymer chain. Increased solubility untangles polymer aggregates into single, dispersed, polymer chains, as we demonstrate here for DAO-PPV in 1,2-dichlorobenzene and at high temperature.

We have observed enhanced optical limiting behavior in solutions of a derivatized fullerene (phenyl-C(61)-butyric acid cholesteryl ester) from 532 to 700 nm. Transient absorption measurements determined the spectral and temporal regions of interest for optical limiting in C(60) and in C(60) derivatives that are due to a reverse saturable absorption mechanism and predicted enhanced limiting at longer wavelengths. Intensity-dependent transmission measurements made at several wavelengths confirmed these results. The increased solubility and the broadened ground-state absorption of the functionalized C(60) make it suitable for use as an optical limiter in the red and the near infrared.

Engineered fullerenes (C(60)) are extensively used for commercial and clinical applications based on their unique physicochemical properties. Such materials have also been recognized as byproducts of many industrial activities. Functionalization of C(60) may significantly influence the nature of its interactions with biological systems, impacting its applications and raising uncertainties about its health effects. In the present study, we compared the bioimpact of two chemically modified fullerene derivatives, hexa carboxyl fullerene adduct (Hexa-C(60)) and tris carboxyl fullerene adduct (tris-C(60)) to pristine fullerene C(60) encapsulated with gamma (gamma)-cyclodextrin C(60) (CD-C(60)), using human cutaneous epithelial cells (HEK) to simulate possible applications and occupational dermal exposure route. We report, for the first time, the discovery of premature senescence as a potential endpoint of nanomaterial elicited biological effects, providing a new paradigm for nanoparticle-induced toxicity in human cells. Moreover, this response appeared to be functionalization specific, in that, only tris-C(60) induced senescence. We investigated key biological responses, such as cellular viability, intracellular ROS generation, cell proliferation and cell cycle responses. Our results indicate that the often observed 'anti-apoptotic' function of fullerene derivatives may be independent of their 'ROS scavenging' role as previously reported. We discovered that the tris-C(60)-induced responses were associated with G(0)/G(1) cell cycle arrest and cellular senescence. On further evaluation of the molecular mechanisms underlying the senescent response, a significant decrease in the expression levels of HERC5 was noted. HERC5 is a ubiquitin ligase of the HERC family and is implicated to be involved in innate immune responses to viral and bacterial infections.

In this work we build on prior studies of the novel water-soluble cationic conjugated polymer known as "P2" (poly{2,5-bis[3-( N, N, N-triethylammonium bromide)-1-oxapropyl]-1,4-phenylenevinylene}) with a focus on its incorporation into thin films for such applications as photovoltaics or electroluminescent devices. Multilayer assemblies were constructed using P2, the anionic surfactant sodium dodecyl sulfate (SDS), and the polyanion poly(sodium 4-styrene-sulfonate) (PSS) using the technique of layer-by-layer electrostatic self-assembly (LBL-ESA). SDS was observed to affect the layer thicknesses and absorbance characteristics of the films. We show that the optical properties and photo-oxidative resistance can be improved by varying the SDS content in the assemblies. Specifically, the surfactant-complexed poly( p-phenylenevinylene) (PPV) shows an enhanced absorption at longer wavelengths as well as improved photostability. Therefore, our work may have broad implications on the development of stable PPV-based materials in general and their efficient integration into thin films technologies.

In this work, we investigate the emission and absorbance properties of the novel water-soluble cationic conjugated polymer poly{2,5-bis[3-(N,N,N-triethylammonium bromide)-1-oxapropyl]-1,4-phenylenevinylene}, denoted here as P2, in the presence of varying amounts of the anionic surfactant sodium dodecylsulfate (SDS). We show that the absolute photoluminescence quantum efficiency (PLQE), the absorption wavelength, and the emission wavelength of an aqueous solution of P2 can be adjusted according to the surfactant/polymer ratio in aqueous solution. In particular, we show that the addition of SDS to P2 increases the polyelectrolyte's PLQE to approximately 40%. An observed red shift in the emission spectra upon addition of the surfactant is attributed to the reduction in electrostatic repulsive interactions between side chains that minimize the benzene ring twisting along the backbone structure. At the surfactant's critical micelle concentration, the P2 chains wrap around the outer surface of the SDS micelles. This work has implications on the development of new stable poly(p-phenylenevinylene)-based photovoltaic and electroluminescent materials with tunable optical properties.

Preparation de melanges PT/PS, PPy/PS,PT/PC et PPY/PC pour polymerisation electrolytique du thiophene ou de pyrrole sur des electrodes recouvertes de PS ou de PC et mesure de leur conductivite en fonction de leur composition. La meilleure conductivite du melange PPy/PC est attribuee a la formation de liaisons hydrogenes, en accord avec les resultats de TGA, DSC et IR

We report here the synthesis and characterization of two new conjugated polymers: poly{2,5-bis[3-(N,N-diethylammonium acetate)-1-oxapropyl]-1,4-phenylenevinylene} (P1') and poly{2,5-bis[3-(N,N,N-triethylammonium bromide)-1-oxapropyl]-1,4-phenylenevinylene} (P2). Both polymers exhibit unique pH-dependent optical properties in aqueous solution. These pH-dependent optical properties are attributed to the mutual electrostatic repulsions of positive charges pendent on the benzene rings. This electrostatic repulsion leads to an increased or decreased torsional angle in the conjugated backbone, thus affecting the effective conjugation length of these polymers. The UV-vis spectra of P1 in various pH solutions exhibit a near-isosbestic point, which indicates changes in the composition of the two distinct conformations (the charged and the neutral forms). The transition between the highly charged state and the neutral state was clearly observed in the UV-vis and photoluminescence studies on both P1 and P2. This transition is particularly sensitive in the pH range from 6.2 to 7.0, a range that would allow the detection of minor environmental changes. P2 has a quantum efficiency of 14% in water, which is considered to be relatively high among water-soluble PPVs.

This Letter reports the observation of hysteresis in the vortex pinning in a superconductor-ferromagnetic epitaxial nanocomposite consisting of fcc Gd particles incorporated in a Nb matrix. We show that this hysteretic pinning is associated with magnetic reversal losses in the Gd particles and is fundamentally different in origin to pinning interactions previously observed for ferromagnetic particles or other microstructural features.

Manufacturing of 3C (computer, communication and consumer electronics) products toward weight-reduction, thin-wall and minified-size is an inescapable trend for the future 3C industries. As a result, impact-induced damage becomes a great concern in design engineer regarding the robustness and reliability of 3C products. Traditionally, the mechanical performance of 3C product is mainly verified through physical drop test, which vast investment in cost and time is spent on proto-type model and development of experimental setup. It is necessary to know the impact force, acceleration and impact orientation when the products contact the ground. In this study, a physical drop/impact test system had setup. The drop/impact test system, associated with impact orientation control mechanism, fast speed visual surveillance system, and data acquisition/processing system is completed. A set of correlated spatial equations provides a relative accurate methodology to estimate the impact instance orientation, which is a key factor to structure design from impact damage. Based on the current study, it shows that drop/impact simulation plays an important role in design requirement of thin-wall products. It was found that this system provides excellent repeatability on impact angle control and spatial orientation analysis. Drop test for mouse housing is carried out at four different designed orientations and 50 tests are performed in each drop orientation. As long as the repeatability can be well controlled, a single frame, instead of continuous frames as taken by the HSC, is able to serve such a purpose with certain confidence levels. The repeatability of this tester is verified by four different drop orientation tests. The statistics show that the repeatability of the current drop tester can be achieved at 97.2% within plusmn5deg from a total of 200 drops. Finally, the maximum accelerations from the accelerometer outputs also indicate that those tests are very consistent. Therefore, it is crucial for the CAE users to understand the correlation effects between the simulation variation (such as structural stress/strain, impact force and acceleration), impact parameters (such as material definition, impact instance angle, part connection definition, etc.) and structural mechanical performance. Drop-impact performance should be well recognized during the product design. Experimental validation, robust modeling, analysis skill, and material property databases are the key factors to a future application. Accurate control on impact angle variation, impact acceleration, and numerical simulation are investigated and presented.

Current state-of-the-art photovoltaics utilize high purity single-crystal semiconductors grown by sophisticated, high temperature crystal-growth processes. Alternative emerging solar cell technologies based on solution-processed materials promise to deliver power at lower cost, but so far have had limited success due to the presence of defects in the bulk and at the grain boundaries. Improving the crystal size and quality of solution-processed films could lead to unprecedented improvements in photovoltaic performance. However, large-scale crystal growth is challenging in solution-based deposition where molecular kinetics are limited by the low processing temperature. Here, for the first time we demonstrate organometallic perovskites thin-films composed of extra-ordinarily large crystalline grains (1-2 mm), fabricated using a new processing technique. The increase in the grain-size directly correlates to a dramatic increase in the efficiency, as a direct consequence of increased charge carrier mobility and reduction in defect densities. Our measured efficiency values approach ~18%, which is among the highest reported. These devices are extremely robust, exhibiting no degradation with voltage sweep direction or the rate at which the voltage was scanned. We anticipate that this technique for growing high quality large-area crystals at low temperature with low defect concentration will be universally applicable to a wide variety of other material systems thus providing a solution to a long-standing scientific challenge of overcoming polydispersity, defects and grain boundary recombination in solution-processed thin-films. From the perspective of the global photovoltaics community, these results are expected to lead the field towards the synthesis of wafer-scale crystalline perovskites necessary for the fabrication of high-efficiency single-junction and hybrid (semiconductor and perovskite) tandem planar cells. In addition, I will also discuss design principles that govern the photostability in these systems.

Water-soluble, same charged, cationic conjugated poly(phenylenevinylene) (PPV) and cationic fullerenes were complexed with negatively charged single stranded DNA and double stranded DNA via electrostatic and pi-pi interactions. The photoinduced charge transfer complex (PPV/DNA/C60) has a charge transfer and separation efficiencies at least comparable to those observed from oppositely charged, cationic PPV and anionic fullerene. DNA serves as a template that straightens the PPV chain conformation which leads to an enhanced quantum yield. Meanwhile, DNA allows incorporation of C60 by overcoming the electrostatic repulsion between PPV and C60. While oppositely charge donor and acceptor molecules feature charge transfer in the form of static quenching, for DNA-assisted charge transfer complexes, the charge transfer proceeds as a combination of static and dynamic quenching for ssDNA and purely dynamic for dsDNA.

In this work, we demonstrate for the first time the novel electrochromic devices based on a series of ambipolar polyimidothioethers (PITEs) driven by state-of-the-art solution-processed perovskite solar cells. These devices with high color contrast and fast response time can have a low operating voltage, less than one volt. The electrochromic PITEs were prepared from new triphenylamine-based bismaleimides and commercial dithiols via Michael polyaddition. These polymers were readily soluble in various organic solvents and showed thermal stability associated with high glass-transition temperatures. The perovskite solar cell developed in our lab has a power conversion efficiency greater than 15% and open circuit voltage of 0.8-0.9 V, rivals the efficiency and cost of silicon solar cells in converting sunlight to electricity. Combined the innovative developments of both perovskite photovoltaics and ambipolar electrochromic materials, we have achieved a novel design of smart materials devices with strong commercial implications.

We report the synthesis of a series of amphiphilic molecular building blocks that can be self-assembled at the air-water interface to form two- and three-dimensional nanostructures with tunable optoelectronic properties. Compression of these molecular building blocks using the Langmuir-Blodgett method gives rise to monolayer and multilayer thin films with different packing densities and electronic properties that are tunable due to varying pi-pi (hydrophobic) interactions. Depending on the noncovalent interaction between chromophores, we observe a transition toward denser packing with increasing number of phenylene ethynylene repeat units. Additionally, we use quantum-chemical simulations to help determine the excited-state electronic structure, intermolecular interactions, and packing trends. Our results demonstrate that the interplay between dipole-dipole and pi-pi interactions dominates the formation of thin films with various packing densities and determines the associated optical properties.

Mixed surfactant-polyelectrolyte multilayer films were fabricated by both ionic self-assembly and spin assembly. A polycation [PEI = poly(ethylenimine)] was deposited from a dilute solution, while a polyanion (PAZO = poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt]) was deposited from a mixture containing a fixed concentration of polyanion and various concentrations of the anionic surfactant sodium dodecyl sulfate (SDS). Coadsorption of SDS and PAZO onto PEI layers was observed using both deposition methods and attributed to strong PEI-SDS interactions and entropic factors. Increasing the concentration of SDS resulted in films containing progressively less adsorbed PAZO. No further reduction in the amount of adsorbed PAZO was observed above the SDS critical micelle concentration. We attribute the film growth behavior to a fast adsorption of SDS onto PEI, followed by a slower adsorption of PAZO onto the remaining unoccupied binding sites. We observe that SDS interpenetrates throughout the PAZO and PEI layers, increasing the surface hydrophobicity of both. We observed similar behavior for both ionically self-assembled and spin-assembled systems.

We report here the fabrication and characterization of solid-state, conducting polymer actuators. The electrochemical activity of polyaniline (PANI) thin film coated with solid-state polyelectrolyte is very similar to the polyaniline thin film in an aqueous solution. The solid-state actuator is adhered to a lever arm of an force transducer and the force generation is measured. The force generated by the actuator is found to be length dependent. However, the overall torques generated by the actuators with different lengths remains essentially the same. The effect of stimulation signals such as voltage, current, on the bending angle and displacement is also studied using square wave potential

Most polymer electroluminescent devices to date are represented as tunnel diodes and operate under direct‐current (dc) driving field. Here we report the fabrication of symmetrically configured alternating‐current (ac) light‐emitting (SCALE) devices based on conjugated polymers. The new devices consist of an emissive polymer layer sandwiched between two redox polymer layers. This configuration enables the SCALE devices to work under both forward and reverse dc bias as well as in ac modes. The nearly ohmic electrode/redox polymer contacts improve the charge injection efficiency significantly and make the SCALE device operation insensitive to electrode work functions. Symmetric operation supports the key role of redox polymer/emissive polymer interface states.

We report here the fabrication and characterization of solid-state conducting polymer actuators. The electrochemical activity of polyaniline (PANI) thin film coated with solid-state polyelectrolyte is very similar to the polyaniline thin film in an aqueous solution. The solid-state actuator is adhered to a lever arm of a force transducer and the force generation is measured in real time. The force generated by the actuator is found to be length dependent. However, the overall torque generated by the actuators with different lengths remains essentially the same. The effect of stimulation signals such as voltage, and current, on the bending angle and displacement is also studied using square wave potential.