Controlling film morphology in conjugated polymer:fullerene blends with surface patterning

We study the effects of patterned surface chemistry on the microscale and nanoscale morphology of solution-processed donor/acceptor polymer-blend films. Focusing on combinations of interest in polymer solar cells, we demonstrate that patterned surface chemistry can be used to tailor the film morphology of blends of semiconducting polymers such as poly-[2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene] (MDMO-PPV), poly-3-hexylthiophene (P3HT), poly[(9,9-dioctylflorenyl-2,7-diyl)-co-benzothiadiazole)] (F8BT), and poly(9,9-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylendiamine) (PFB) with the fullerene derivative, [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM). We present a method for generating patterned, fullerene-terminated monolayers on gold surfaces and use microcontact printing and Dip-Pen Nanolithography (DPN) to pattern alkanethiols with both micro- and nanoscale features. After patterning with fullerenes and other functional groups, we backfill the rest of the surface with a variety of thiols to prepare substrates with periodic variations in surface chemistry. Spin coating polymer:PCBM films onto these substrates, followed by thermal annealing under nitrogen, leads to the formation of structured polymer films. We characterize these films with Atomic Force Microscopy (AFM), Raman spectroscopy, and fluorescence microscopy. The surface patterns are effective in guiding phase separation in all of the polymer:PCBM systems investigated and lead to a rich variety of film morphologies that are inaccessible with unpatterned substrates. We demonstrate our ability to guide pattern formation in films thick enough to be of interest for actual device applications (up to 200 nm in thickness) using feature sizes as small as 100 nm. Finally, we show that the surface chemistry can lead to variations in film morphology on length scales significantly smaller than those used in generating the original surface patterns. The variety of behaviors observed and the wide range of control over polymer morphology achieved at a variety of different length scales have important implications for the development of bulk heterojunction solar cells.     

Effects of cochlear implant processing and fundamental frequency on the intelligibility of competing sentences

Speech perception in the presence of another competing voice is one of the most challenging tasks for cochlear implant users. Several studies have shown that (1) the fundamental frequency (F0) is a useful cue for segregating competing speech sounds and (2) the F0 is better represented by the temporal fine structure than by the temporal envelope. However, current cochlear implant speech processing algorithms emphasize temporal envelope information and discard the temporal fine structure. In this study, speech recognition was measured as a function of the F0 separation of the target and competing sentence in normal-hearing and cochlear implant listeners. For the normal-hearing listeners, the combined sentences were processed through either a standard implant simulation or a new algorithm which additionally extracts a slowed-down version of the temporal fine structure (called Frequency-Amplitude-Modulation-Encoding). The results showed no benefit of increasing F0 separation for the cochlear implant or simulation groups. In contrast, the new algorithm resulted in gradual improvements with increasing F0 separation, similar to that found with unprocessed sentences. These results emphasize the importance of temporal fine structure for speech perception and demonstrate a potential remedy for difficulty in the perceptual segregation of competing speech sounds.     

Crystal chemistry of thorium nitrates and chromates

The structures and infrared spectra of six novel thorium compounds are reported. Th(NO₃)₂(OH)₂(H₂O)₂ (1) crystallizes in space group C2/c, a=14.050(1), b=8.992(7), c=5.954(5) Å, β=101.014(2)°. K₂Th(NO₃)₆ (2), P-3, a=13.606(1), c=6.641(6) Å. (C₁₂H₂₈N)₂Th(NO₃)₆ (3), P2₁/c, a=14.643(4), b=15.772(5), c=22.316(5) Å, β=131.01(1)°. KTh(NO₃)₅(H₂O)₂ (4), P2₁/c, a=10.070(8), b=12.731(9), c=13.231(8) Å, β=128.647(4)°. Th(CrO₄)₂(H₂O)₂ (5), P2₁/n, a=12.731(1), b=9.469(8), c=12.972(1) Å, β=91.793(2)°. K₂Th₃(CrO₄)₇(H₂O)₁₀ (6), Ama2, a=19.302(8), b=15.580(6), c=11.318(6) Å. The coordination polyhedra about Th in these structures are diverse. Th is coordinated by 9 O atoms in 5 and 6, seven of which are from monodentate (CrO₄) tetrahedra and two are (H₂O). The Th in compound 1 is coordinated by ten O atoms, four of which are O atoms of two bidentate (NO₃) triangles and six of which are (OH) and (H₂O). In compounds 2, 3 and 4 the Th is coordinate by 12 O atoms. In 2 and 3 there are six bidentate (NO₃) triangles, and in 4 ten of the O atoms are part of five bidentate (NO₃) triangles and the others are (H₂O) groups. The structural units of these compounds consist of a chain of thorium and nitrate polyhedra (1), isolated thorium hexanitrate clusters (2, 3), an isolated thorium pentanitrate dihydrate cluster (4), and a sheet (6) and framework (5) of thorium and chromate polyhedra. These structures illustrate the complexity inherent in the crystal chemistry of Th.     

Contact forces at the sliding interface: mixed versus pure model alkane monolayers

Classical molecular dynamics simulations of an amorphous carbon tip sliding against monolayers of n-alkane chains are presented. The tribological behavior of tightly packed, pure monolayers composed of chains containing 14 carbon atoms is compared to mixed monolayers that randomly combine equal amounts of 12- and 16-carbon-atom chains. When sliding in the direction of chain cant under repulsive (positive) loads, pure monolayers consistently show lower friction than mixed monolayers. The distribution of contact forces between individual monolayer chain groups and the tip shows pure and mixed monolayers resist tip motion similarly. In contrast, the contact forces "pushing" the tip along differ in the two monolayers. The pure monolayers exhibit a high level of symmetry between resisting and pushing forces which results in a lower net friction. Both systems exhibit a marked friction anisotropy. The contact force distribution changes dramatically as a result of the change in sliding direction, resulting in an increase in friction. Upon continued sliding in the direction perpendicular to chain cant, both types of monolayers are often capable of transitioning to a state where the chains are primarily oriented with the cant along the sliding direction. A large change in the distribution of contact forces and a reduction in friction accompany this transition.     

Infrared laser spectroscopy of jet cooled cobalt tricarbonyl nitrosyl

Rotationally resolved infrared absorption spectra for the 1(0)(1) band of jet cooled cobalt tricarbonyl nitrosyl have been observed and analyzed. Several longitudinal modes of a Pb-salt diode laser were utilized to measure 105 rovibrational transitions for this particular vibrational band centered near 2112 cm(-1). Spectra were optimized using both argon and helium carrier gases and these experiments eventually led to rovibrational transitions being assigned to four different K subbands, specifically the K = 0, 3, 6, and 9 subbands. An iterative least-squares analysis of the spectroscopic data yielded the following molecular parameters nu0 = 2111.7457(9) cm(-1), B0 = 0.034747(12) cm(-1), B1 = 0.034695(15) cm(-1), C1 = 0.03380(9) cm(-1), and D1K = 6.3(9) x 10(-6) cm(-1) (where 3sigma uncertainties are listed in parenthesis).     

Computational studies of electron‐transfer processes in old yellow enzyme

Old Yellow Enzyme (OYE) is a flavoenzyme that was first isolated from brewer's bottom yeast. Homologues have been identified in other strains of yeast, bacteria, and plants. In plants, the OYE homologue functions enzymatically in the synthesis of plant hormones, but the biological function of OYE in yeast is still unknown. Flavin mononucleotide (FMN) is the cofactor that is noncovalently bound in the enzyme. OYE binds several phenolic ligands that serve as models for reactive biological substrates. These complexes have broad long‐wavelength absorption bands, which have been ascribed to charge‐transfer interactions, with the phenolate anion acting as the electron donor and the FMN as the acceptor [Abramovitz, A. S.; Massey, V. J Bio Chem 1976, 251, 5327–5336]. The computational characterization of these electronic transitions in the active site will help in understanding the biological processes in the enzyme. It was found that at several levels of computational methods, and through computationally mutating relevant amino acids, a charge‐transfer process is occurring. This result agrees with previous experimental work and is consistent with all ultraviolet–visible spectrophotometric data. The preliminary results for the computational studies of these electron‐transfer processes will be presented. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Investigation of capillary electrophoresis-laser induced fluorescence as a tool in the characterization of sewage effluent for fluorescent acids: determination of salicylic acid

The investigation of emerging contaminant issues is a proactive effort in environmental analysis. As a part of this effort, sewage effluent is of current analytical interest because of the presence of pharmaceuticals and their metabolites and personal care products. The environmental impact of these components is still under investigation but their constant perfusion into receiving waters and their potential effect on biota is of concern. This paper examines a tool for the characterization of sewage effluent using capillary electrophoresis-laser induced fluorescence (CE-LIF) with a frequency-doubled laser operated in the ultraviolet (UV). Fluorescent acidic analytes are targeted because they present special problems for techniques such as gas chromatography-mass spectrometry (GC-MS) but are readily accessible to CE-LIF. As an example of the application of this tool, salicylic acid is determined near the 100 ng/L (7 x 10(-10) M) level in sewage effluent. Salicylic acid is a metabolite of various analgesics. Relatively stable in the environment, it is a common contaminant of municipal sewage systems. Salicylic acid was recovered from freshly collected samples of the effluent by liquid-liquid extraction. Confirmation of identity was by electron ionization GC-MS after conversion of the salicylic acid to the methyl ester by means of trimethylsilyldiazomethane. CE-LIF in the UV has revealed more than 50 individual peaks in the extract and a background response that suggests a large and indeterminate number of additional compounds are present. These data together with complementary techniques provide information on the complexity and components in these effluent streams.     

Cochlear implant speech recognition with speech maskers

Speech recognition performance was measured in normal-hearing and cochlear-implant listeners with maskers consisting of either steady-state speech-spectrum-shaped noise or a competing sentence. Target sentences from a male talker were presented in the presence of one of three competing talkers (same male, different male, or female) or speech-spectrum-shaped noise generated from this talker at several target-to-masker ratios. For the normal-hearing listeners, target-masker combinations were processed through a noise-excited vocoder designed to simulate a cochlear implant. With unprocessed stimuli, a normal-hearing control group maintained high levels of intelligibility down to target-to-masker ratios as low as 0 dB and showed a release from masking, producing better performance with single-talker maskers than with steady-state noise. In contrast, no masking release was observed in either implant or normal-hearing subjects listening through an implant simulation. The performance of the simulation and implant groups did not improve when the single-talker masker was a different talker compared to the same talker as the target speech, as was found in the normal-hearing control. These results are interpreted as evidence for a significant role of informational masking and modulation interference in cochlear implant speech recognition with fluctuating maskers. This informational masking may originate from increased target-masker similarity when spectral resolution is reduced.