Light-enhanced catalysis by pyridoxal phosphate-dependent aspartate aminotransferase

The mechanisms of pyridoxal 5'-phosphate (PLP)-dependent enzymes require substrates to form covalent "external aldimine" intermediates, which absorb light strongly between 410 and 430 nm. Aspartate aminotransferase (AAT) is a prototypical PLP-dependent enzyme that catalyzes the reversible interconversion of aspartate and α-ketoglutarate with oxalacetate and glutamate. From kinetic isotope effects studies, it is known that deprotonation of the aspartate external aldimine C(α)-H bond to give a carbanionic quinonoid intermediate is partially rate limiting in the thermal AAT reaction. We show that excitation of the 430-nm external aldimine absorption band increases the steady-state catalytic activity of AAT, which is attributed to the photoenhancement of C(α)-H deprotonation on the basis of studies with Schiff bases in solution. Blue light (250 mW) illumination gives an observed 2.3-fold rate enhancement for WT AAT activity, a 530-fold enhancement for the inactive K258A mutant, and a 58600-fold enhancement for the PLP-Asp Schiff base in water. These different levels of enhancement correlate with the intrinsic reactivities of the C(α)-H bond in the different environments, with the less reactive Schiff bases exhibiting greater enhancement. Time-resolved spectroscopy, ranging from femtoseconds to minutes, was used to investigate the nature of the photoactivation of C(α)-H bond cleavage in PLP-amino acid Schiff bases both in water and bound to AAT. Unlike the thermal pathway, the photoactivation pathway involves a triplet state with a C(α)-H pK(a) that is estimated to be between 11 and 19 units lower than the ground state for the PLP-Val Schiff base in water.     

Fourier transformed infrared spectral investigations of molecular interactions in propionic acid–2-propanol binary system

FTIR spectra of propionic acid (PA), 2-propanol (PROH) and its binary mixtures with varying molefraction of the PA were recorded in the region 500–3500 cm^?1, to investigate the formation of hydrogen bonded complexes in a mixed system. The observed features in ν(CO), ν(CO) and δ(COH) of PA, ν(CO) of PROH and δ(COH) of PA + PROH have been explained in terms of the hydrogen bonding interactions between PROH and PA and dipole–dipole interaction. The dipole moment derivative for the above mentioned vibrational modes have also been predicted from the integrated absorbance. The intrinsic linewidth for the vibrational modes ν(CO) and δ(COH) of PA has been elucidated using Bondarev and Mardaeva model.     

Quantitative assessment of moisture damage for cacao bean quality using two-dimensional gas chromatography combined with time-of-flight mass spectrometry and chemometrics

Quality control of cacao beans is a significant issue in the chocolate industry. In this report, we describe how moisture damage to cacao beans alters the volatile chemical signature of the beans in a way that can be tracked quantitatively over time. The chemical signature of the beans is monitored via sampling the headspace of the vapor above a given bean sample. Headspace vapor sampled with solid-phase micro-extraction (SPME) was detected and analyzed with comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GC × GC–TOFMS). Cacao beans from six geographical origins (Costa Rica, Ghana, Ivory Coast, Venezuela, Ecuador, and Panama) were analyzed. Twenty-nine analytes that change in concentration levels via the time-dependent moisture damage process were measured using chemometric software. Biomarker analytes that were independent of geographical origin were found. Furthermore, prediction algorithms were used to demonstrate that moisture damage could be verified before there were visible signs of mold by analyzing subsets of the 29 analytes. Thus, a quantitative approach to quality screening related to the identification of moisture damage in the absence of visible mold is presented.     

Classification of behavior using vocalizations of Pacific white-sided dolphins (Lagenorhynchus obliquidens)

Surface behavior and concurrent underwater vocalizations were recorded for Pacific white-sided dolphins in the Southern California Bight (SCB) over multiple field seasons spanning 3 years. Clicks, click trains, and pulsed calls were counted and classified based on acoustic measurements, leading to the identification of 19 key call features used for analysis. Kruskal-Wallis tests indicated that call features differ significantly across behavioral categories. Previous work had discovered two distinctive click Types (A and B), which may correspond to known subpopulations of Pacific white-side dolphins in the Southern California Bight; this study revealed that animals producing these different click types also differ in both their behavior and vocalization patterns. Click Type A groups were predominantly observed slow traveling and milling, with little daytime foraging, while click Type B groups were observed traveling and foraging. These behavioral differences may be characteristic of niche partitioning by overlapping populations; coupled with differences in vocalization patterns, they may signify that these subpopulations are cryptic species. Finally, random forest decision trees were used to classify behavior based on vocalization data, with rates of correct classification up to 86%, demonstrating the potential for the use of vocalization patterns to predict behavior.     

Masked auditory thresholds in three species of birds, as measured by the auditory brainstem response (L)

Auditory brainstem responses (ABRs) were recorded in adult budgerigars, canaries, and zebra finches in quiet and in three levels of white noise for tone stimuli between 1 and 4 kHz. Similar to behavioral results, masked ABR thresholds increased linearly with increasing noise levels. When the three species are considered together, ABR-derived CRs were higher than behavioral CRs by 18-23 dB between 2 and 4 kHz and by about 30 dB at 1 kHz. This study clarifies the utility of using ABRs for estimating masked auditory thresholds in natural environmental noises in species that cannot be tested behaviorally.     

Inhomogeneity-free heteronuclear iMQC

Intermolecular dipolar interactions between proton and carbon spins can be used to indirectly detect carbon spectra with high sensitivity. In this communication, we present a modified sequence that, in addition to the high sensitivity of heteronuclear intermolecular multiple quantum coherence (iMQC) experiments, retains the line narrowing capability characteristic of homonuclear zero-quantum coherences. We demonstrate that this sequence can be used to obtain high resolution (13)C spectra in the presence of magnetic field inhomogeneities, both for thermal and hyperpolarized samples, and discuss applications to water-hyperpolarized carbon imaging.     

Leading US nano-scientists’ perceptions about media coverage and the public communication of scientific research findings

Despite the significant increase in the use of nanotechnology in academic research and commercial products over the past decade, there have been few studies that have explored scientists’ perceptions and attitudes about the technology. In this article, we use survey data from the leading U.S. nano-scientists to explore their perceptions about two issues: the public communication of research findings and media coverage of nanotechnology, which serves as one relatively rapid outlet for public communication. We find that leading U.S. nano-scientists do see an important connection between the public communication of research findings and public attitudes about science. Also, there is a connection between the scientists’ perceptions about media coverage and their views on the timing of public communication; scientists with positive attitudes about the media are more likely to support immediate public communication of research findings, while others believe that communication should take place only after research findings have been published through a peer-review process. We also demonstrate that journalists might have a more challenging time getting scientists to talk with them about nanotechnology news stories because nano-scientists tend to view media coverage of nanotechnology as less credible and less accurate than general science media coverage. We conclude that leading U.S. nano-scientists do feel a sense of responsibility for communicating their research findings to the public, but attitudes about the timing and the pathway of that communication vary across the group.     

Voice Training and Changing Weight—Are They Reflected in Speaking Fundamental Frequency, Voice Range, and Pitch Breaks of 13-Year-Old Girls? A Longitudinal Study

Objective

Assessment of the voice-change progress of 20 girls (12–13 years) over 1 year by observing changes in speaking fundamental frequency (SFo), voice range, and register pitch breaks in the context of weight, height, voice training, and self-perception.

Study Design

One-year longitudinal collective case study.

Method

Twenty girls were recorded at the beginning and end of a year; nine girls were recorded another three times. SFo, vocal range, and characteristics were analyzed and interactions between these data assessed against weight and height to indicate pubertal development, and to test the hypothesis that changes in weight, height, SFo, and pitch breaks were related. Effects of training and the girls' self-perception of their voice use were also assessed.

Results

Vocal characteristics changed as the girls passed through different weight ranges. During 47.5–52.4 kg (called band 2) and 52.4–57.5 kg (band 3), there was progressive contraction of vocal range and in some girls a slight rise in SFo between recording times 1 and 5. Both high- and low-pitch breaks were present in 45% of girls' voices. Girls in band 4 (<57.5 kg) had an increased vocal range, and pitch breaks in vocal-range areas that indicated the development of adult vocal registers. In this study, voice-trained girls were heavier, had higher SFo, used wider speech-range inflection, had a higher vocal range, and greater voice-use confidence; all girls lost confidence in their voice use over the year.

Conclusions

In this longitudinal study of twenty 13-year-old girls, voice changes in SFo, vocal range, and pitch-break frequency were synchronous with certain weight ranges. Girls with training registered higher maximum phonational frequency and were more confident in their voice use than girls without training.     

Assessing views of coaching via a video-based tool

Mathematics coaches represent a unique group of didacticians, or individuals who work with practicing teachers. Twenty-eight mathematics coaches participated in this exploratory study, which used video viewing to examine the coach–teacher dynamic. To gather data about participants’ views of effective coaching practices, we developed the Video Assessment of Coaching instrument, which provided coaches with opportunities to express their views of effective practice and implementation. The participants expressed views of effective coaching that often did not align with those of coaching authors. The significance of this research lies in its efforts to document the views that mathematics coaches develop as practitioners, as an early step in the examination of the relationships between the views of coaches and coaches’ effectiveness in improving teacher practice, knowledge, and attitudes.