TDDFT study of one- and two-photon absorption properties: donor-pi-acceptor chromophores

We report a comprehensive time-dependent density functional theory (TDDFT) study of one-photon and two-photon absorption (OPA and TPA, respectively) spectra for donor-pi-acceptor molecules. The calculated excitation energies were generally shown to be in good agreement with experiment, particularly when compared to results from measurements carried out in a nonpolar solvent, although the oscillator strengths were overestimated in some cases. Calculated TPA cross sections applying the two-state approximation were shown to be highly dependent on the form of the line-shape function used. Although a good agreement with experimental TPA spectra was generally observed, the wide range in the experimentally measured values and lack of systematic experimental data on solvent effects limited a detailed comparison as yet.     

Speech intelligibility and spatial release from masking in young children

Children between the ages of 4 and 7 and adults were tested in free field on speech intelligibility using a four-alternative forced choice paradigm with spondees. Target speech was presented from front (0 degrees); speech or modulated speech-shaped-noise competitors were either in front or on the right (90 degrees). Speech reception thresholds were measured adaptively using a three-down/one-up algorithm. The primary difference between children and adults was seen in elevated thresholds in children in quiet and in all masked conditions. For both age groups, masking was greater with the speech-noise versus speech competitor and with two versus one competitor(s). Masking was also greater when the competitors were located in front compared with the right. The amount of masking did not differ across the two age groups. Spatial release from masking was similar in the two age groups, except for in the one-speech condition, when it was greater in children than adults. These findings suggest that, similar to adults, young children are able to utilize spatial and/or head shadow cues to segregate sounds in noisy environments. The potential utility of the measures used here for studying hearing-impaired children is also discussed.     

The role of head-induced interaural time and level differences in the speech reception threshold for multiple interfering sound sources

Three experiments investigated the roles of interaural time differences (ITDs) and level differences (ILDs) in spatial unmasking in multi-source environments. In experiment 1, speech reception thresholds (SRTs) were measured in virtual-acoustic simulations of an anechoic environment with three interfering sound sources of either speech or noise. The target source lay directly ahead, while three interfering sources were (1) all at the target's location (0 degrees,0 degrees,0 degrees), (2) at locations distributed across both hemifields (-30 degrees,60 degrees,90 degrees), (3) at locations in the same hemifield (30 degrees,60 degrees,90 degrees), or (4) co-located in one hemifield (90 degrees,90 degrees,90 degrees). Sounds were convolved with head-related impulse responses (HRIRs) that were manipulated to remove individual binaural cues. Three conditions used HRIRs with (1) both ILDs and ITDs, (2) only ILDs, and (3) only ITDs. The ITD-only condition produced the same pattern of results across spatial configurations as the combined cues, but with smaller differences between spatial configurations. The ILD-only condition yielded similar SRTs for the (-30 degrees,60 degrees,90 degrees) and (0 degrees,0 degrees,0 degrees) configurations, as expected for best-ear listening. In experiment 2, pure-tone BMLDs were measured at third-octave frequencies against the ITD-only, speech-shaped noise interferers of experiment 1. These BMLDs were 4-8 dB at low frequencies for all spatial configurations. In experiment 3, SRTs were measured for speech in diotic, speech-shaped noise. Noises were filtered to reduce the spectrum level at each frequency according to the BMLDs measured in experiment 2. SRTs were as low or lower than those of the corresponding ITD-only conditions from experiment 1. Thus, an explanation of speech understanding in complex listening environments based on the combination of best-ear listening and binaural unmasking (without involving sound-localization) cannot be excluded.     

Efficient synthesis of B-alkylated oxazaborolidines derived from ephedrine and norephedrine

[reaction: see text] Representative B-butyl- and B-methyl-1,3,2-oxazaborolidines derived from ephedrine and norephedrine were prepared in good yield and excellent purity by one-pot treatment of B-H oxazaborolidines with the corresponding organolithium reagent and subsequent hydrolysis of the cyclic borohydride intermediate with anhydrous ammonium chloride.     

Effect of fluorine in Li1.27Cr0.2Mn0.53O2 cathode for secondary lithium batteries

Fluorine substituted Li_1.27Cr_0.2Mn_0.53O₂ electrode, prepared by sol–gel method, was investigated in the present work. Thermal analysis was done on this cathode material and found to be thermally stable with a loss of weight near 300 °C. Influence of fluorine substitution on the structural and electrochemical properties of the Li_1.27Cr_0.2Mn_0.53O₂ electrode was studied by X-ray diffraction (XRD) and field emission scanning electron microscope. XRD pattern of the fluorine-doped Li_1.27Cr_0.2Mn_0.53O₂ cathode material quenched at 900 °C indicates a phase pure material. The charge–discharge profile of the prepared cathode material showed that the fluorine substitution for oxygen in the cathode material resulted in improved capacity retention. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006.     

Correlation of charge transport with structural order in highly ordered melt‐crystallized poly(3‐hexylthiophene) thin films

A series of well‐defined poly(3‐hexylthiophene)s (P3HT) of different molecular weight (MW) and high regioregularity was investigated for charge transport properties in as‐cast and melt‐crystallized films. The semicrystalline structure of the P3HT was characterized by X‐ray scattering and Atomic force microscopy. Crystallization by cooling from the melt led to a substantial increase in crystallinity and a stronger alignment of the crystals in comparison to as‐cast films. The increase in crystallinity went along with an increase in hole mobility of up to an order of magnitude as measured by the space charge limited current method. Additionally, the hole mobility depended on the long period of P3HT lamellae and consequently on the MW. In compliance with the long period, the charge carrier mobility first increased with the MW before decreasing again at the onset of chain folding. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 943–951     

Investigation of the interaction mechanism of the recombinant human antibody MDJ8 and its fragments with chromatographic apatite phases

The chromatographic behaviour of a recombinant human antibody (IgG₁-subtype, κ-light chain, MW: 149.5 kD, pI: 9.3) was investigated as a function of the buffer pH and buffer type (HEPES, phosphate, borate) on fluoroapatite and hydroxyapatite stationary phases. HEPES buffer was used at pH 7.0, phosphate buffer at pH 8.2 and borate buffer between pH 8.5 and 11. Elution was by a double gradient method of first a salt gradient from 0 to 1 M NaCl in the corresponding buffer, followed by a step gradient to 0.4 M sodium phosphate. Regardless of the pH and buffer type, the antibody eluted in the NaCl gradient; capacity factors decreased with increasing pH. At pH 11 the antibody eluted in the flow-through. Retention was thus dominated by electrostatic interaction throughout the investigated pH-range. Investigation of antibody fragments obtained by papain digestion (fc- and fab-fragments) and deglycosylated fc-fragments showed that the sugar structures had no influence on the chromatographic behaviour. Instead the chromatographic behaviour was dominated by that of the fab-fragment. ζ-Potential measurements verified that the apatite surface bore a negative surface charge in the investigated pH range, while the antibody net surface charge switched from positive to negative as the pH increased. The corresponding isoionic point was a function of both the buffer concentration and the buffer species. However, above a pH of 8.3 the ζ-potential of the antibody generally was negative. Simulations of the molecular electrostatic potential of the antibody and the two fragments revealed the presence of a positively charged patch within the fab-fragment, which only disappeared above a pH of 10. Most likely this patch was responsible for the observed behaviour.     

Measurement of total Zn and Zn isotope ratios by quadrupole ICP-MS for evaluation of Zn uptake in gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss)

This study evaluates the potential use of stable zinc isotopes in toxicity studies measuring zinc uptake by the gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss). The use of stable isotopes in such studies has several advantages over the use of radioisotopes, including cost, ease of handling, elimination of permit requirements, and waste disposal. A pilot study using brown trout was performed to evaluate sample preparation methods and the ability of a quadrupole inductively coupled plasma mass spectrometer (ICP-MS) system to successfully measure changes in the ⁶⁷Zn/⁶⁶Zn ratios for planned exposure levels and duration. After completion of the pilot study, a full-scale zinc exposure study using rainbow trout was performed. The results of these studies indicate that there are several factors that affect the precision of the measured ⁶⁷Zn/⁶⁶Zn ratios in the sample digests, including variations in sample size, endogenous zinc levels, and zinc uptake rates by individual fish. However, since these factors were incorporated in the calculation of the total zinc accumulated by the gills during the exposures, the data obtained were adequate for their intended use in calculating zinc binding and evaluating the influences of differences in water quality parameters.     

Zoospores of Three Arctic Laminariales Under Different UV Radiation and Temperature Conditions: Exceptional Spectral Absorbance Properties and Lack of Phlorotannin Induction

Phlorotannins have often been considered to act as UV-protective compounds in zoospores of brown algae. However, only the absorption characteristics of zoospores under UV exposure have been determined and no data are available on the actual content of phlorotannins or on temperature–UV interactions. Therefore, we determined the absorbance spectra and the phlorotannin contents in zoospore suspensions of three Arctic species ( Saccharina latissima , Laminaria digitata , Alaria esculenta ), and in the media surrounding zoospores after exposure to different radiation (400–700, 320–700, 295–700 nm) and temperature (2–18°C) conditions for 8 h. Absorption typical of phlorotannins with a maximum at 276 nm was monitored in zoospore suspensions as well as in the media surrounding zoospores, but the results depended strongly on radiation treatments and on zoospore densities. Surprisingly, the content of UV-absorbing phlorotannins subsequent to different exposures did not change in any of the three species. The observed exceptional absorption properties could, therefore, not be related to phlorotannin contents. These findings are discussed in light of a strong phlorotannin investment from sporophytes during spore release and a minor UV-protective role of phlorotannins for zoospores of Arctic kelp species.