A study on green organic light-emitting diodes with high electron mobility in hole block and electron transport layers.

The electron mobility and hole blocking ability of BPhen, BCP, and ET137 were investigated by fabricating an electron only device and hole only device, respectively. Although it was observed that ET137 has the highest electron mobility, the device with ET137 as electron transporting layer was unable to obtain high efficiency alone and it was necessary to use a hole blocking layer because of the poor hole blocking ability due to the high-lying HOMO energy level. We fabricated green-emitting phosphorescent devices with various hole blocking layers and electron transporting layers. It was demonstrated that the high electron mobility of the electron transporting layer and hole blocking layer leads to high efficiency in organic light-emitting diodes. The device with BPhen and ET137 as hole blocking layer and electron transporting layer, respectively, showed the best efficiency properties. The maximum values of luminous efficiency, power efficiency, and quantum efficiency were 41.1 cd/A, 26.9 Im/W and 12.4%, respectively.

Combined molecular and supramolecular bottom-up nanoengineering for enhanced nonlinear optical response: experiments, modeling, and approaching the fundamental limit.

The authors study the combination of two independent strategies that enhance the hyperpolarizability of ionic organic chromophores. The first molecular-level strategy is the extension of the conjugation path in the active chromophore. The second supramolecular-level strategy is the bottom-up nanoengineering of an inclusion complex of the chromophore in an amylose helix by self-assembly. The authors study a series of five (dimethylamino)stilbazolium-type chromophores with increasing conjugation length between the (dimethylamino)phenyl donor ring and the pyridinium acceptor ring in conjunction with four amylose helices of differing molecular weights. The first hyperpolarizabilities of the self-assembled inclusion complexes, as determined with frequency-resolved femtosecond hyper-Rayleigh scattering at 800 and 1300 nm, are compared with experimental values for the free chromophores in solution and with theoretical values. While the experimental values for the hyperpolarizability in solution are lower than the theoretically predicted values, an enhancement upon inclusion is observed, with the longest chromophore in the best amylose helix showing an enhancement by one order of magnitude. Molecular modeling of the inclusion of the chromophore suggests that the coplanarity of the two rings is more important than all-trans configuration in the conjugation path. The fundamental limit analysis indicates that the inclusion inside the amylose helix results in an optimal excited-level energy spacing that is responsible for breaching the apparent limit.

One-dimensional energy/electron transfer through a helical channel.

We have synthesized A-D-A-type linear chain chromophores based on oligo(phenylene vinylene) as an electron donor (D) and several electron/energy acceptors (A), which are linked by an alkyl spacer with various lengths and are processed for a helical encapsulation with amylose. Photoinduced electron/energy transfers (eT/ET) of the chromophores are investigated in the presence and absence of the helical encapsulation with respect to D-A distance. Fluorescence intensity of the free chromophores is unusually small, not due to the advancement of eT/ET but most likely to self-quenching by aggregation and/or conformational flexibility in solution. By contrast, the helically encapsulated chromophores exhibit highly efficient eT/ET over a long D-A distance and a well-defined distance effect depending on the acceptor strength.

Super-helix formation induced by cyanine J-aggregates onto random-coil carboxymethyl amylose as template.

The J-aggregation of Cyanine-1dye in the presence of carboxymethyl amylose (CMA) is described. The J-aggregation requires a large excess CMA concentration; the J-band maximum appears in the concentration range, [CMA]/[dye] = 10-50, depending on the degree of substitution (DS) of carboxylation, where [CMA] is the concentration of polymer repeat units. An extraordinarily large induced circular dichroism (CD) is observed from J-aggregates of the achiral cyanine dye in association with a random coil CMA, suggesting that the CMA is transformed into a helix. The magnitude of CD intensity increases with increasing DS of CMA and pH up to neutral (where a maximum J-aggregation occurs), while the CMA-bound dye monomer and H-aggregates (occurring at pH > or = 9) exhibit no induced CD. The trend in the CD intensity (of the J-aggregates) is in parallel with the fluorescence intensity of the J-aggregates. This suggests that binding of the J-aggregates onto the template CMA is sterically controlled by the asymmetric environment of glucose residues (of CMA) so that more twisting power is exerted with increasing DS (of CMA), rendering the cyanine dye/CMA complex a more rigid (a high fluorescence intensity) super-helix. This is also revealed by the AFM image of a long strand.

Solvent and pH effects on fast and ultrasensitive 1,1'-oxalyldi(4-methyl)imidazole chemiluminescence.

Solvent and pH effects on fast and ultrasensitive 1,1'-oxalyldi(4-methyl)imidazole chemiluminescence (OD4MI-CL) were studied. The influences of these two factors on the complex OD4MI-CL reaction are discussed within a conceptual prototype for developing aqueous and non-aqueous capillary electrophoresis (ACE and NACE) devices with OD4MI-CL detection. The reaction channel length and OD4MI yield from the reaction between bis(2,4,6-trichlorophenyl) oxalate (TCPO) and 4-methylimidazole in the channel will be influenced by pH, water volume fraction, and cosolvent properties of the solution. Optimum OD4MI-CL efficiency is observed at pH 6.5 when 1-propanol, which has a low dielectric constant (epsilon = 20.8), is used as the NACE solvent in the separation channel. Water (epsilon = 80.1), the solvent in the ACE separation channel, acts similarly to a high dielectric constant organic solvent in NACE because the disadvantages normally associated with TCPO-CL reactions in water disappear due to the faster OD4MI-CL reaction versus OD4MI decomposition in aqueous solution. Therefore, it is expected that the OD4MI-CL detection system can be used in both NACE and ACE devices without requiring detector modifications. We also conclude that OD4MI-CL detection in NACE and ACE devices will be much more sensitive than the TCPO-CL detection used in current NACE devices.

Solubilization of single-wall carbon nanotubes by supramolecular encapsulation of helical amylose.

We have developed a simple, efficient process for solubilization of single-wall carbon nanotubes (SWNTs) with amylose in aqueous DMSO. This process requires two important conditions, presonication of SWNTs and subsequent amylose treatment in an optimum mixture of DMSO/H2O. The former step separates SWNT bundles, and the latter step provides a maximum cooperative interaction of SWNTs with amylose, leading to the immediate and complete solubilization. The best solvent condition for this is around 10-20% DMSO, in which amylose assumes a random conformation or an interrupted helix. This indicates that the amylose helix is not the prerequisite for encapsulation of SWNTs. The SEM and AFM images of the encapsulated SWNTs manifest loosely twisted ribbons wrapping around SWNTs, which are locally intertwined as a multiple twist, but no clumps of the host amylose are seen on SWNT capsules.

Fast peroxyoxalate chemiluminescence for minimized analytical separation systems.

The maximum intensity, Imax, and time required to reach the maximum emission, taumax, for 1-aminopyrene monitored in 1,1'-oxalyldi-4-methylimidazole (OD4MI) chemiluminescence (CL) reactions are approximately 61 times higher and 16 times faster than their respective values for bis(2,4,6-trichlorophenyl)oxalate (TCPO) CL reactions in the presence of imidazole (ImH).