An Information-Theoretic Approach to Quantitative Analysis of the Correspondence Between Skin Blood Flow and Functional Near-Infrared Spectroscopy Measurement in Prefrontal Cortex Activity.

Effect of Skin blood flow (SBF) on functional near-infrared spectroscopy (fNIRS) measurement of cortical activity proves to be an illusive subject matter with divided stances in the neuroscientific literature on its extent. Whereas, some reports on its non-significant influence on fNIRS time series of cortical activity, others consider its impact misleading, even detrimental, in analysis of the brain activity as measured by fNIRS. This situation is further escalated by the fact that almost all analytical studies are based on comparison with functional Magnetic Resonance Imaging (fMRI). In this article, we pinpoint the lack of perspective in previous studies on preservation of information content of resulting fNIRS time series once the SBF is attenuated. In doing so, we propose information-theoretic criteria to quantify the necessary and sufficient conditions for SBF attenuation such that the information content of frontal brain activity in resulting fNIRS times series is preserved. We verify these criteria through evaluation of their utility in comparative analysis of principal component (PCA) and independent component (ICA) SBF attenuation algorithms. Our contributions are 2-fold. First, we show that mere reduction of SBF influence on fNIRS time series of frontal activity is insufficient to warrant preservation of cortical activity information. Second, we empirically justify a higher fidelity of PCA-based algorithm in preservation of the fontal activity's information content in comparison with ICA-based approach. Our results suggest that combination of the first two principal components of PCA-based algorithm results in most efficient SBF attenuation while preserving maximum frontal activity's information. These results contribute to the field by presenting a systematic approach to quantification of the SBF as an interfering process during fNIRS measurement, thereby drawing an informed conclusion on this debate. Furthermore, they provide evidence for a reliable choice among existing SBF attenuation algorithms and their inconclusive number of components, thereby ensuring minimum loss of cortical information during SBF attenuation process.

Nickel-Catalyzed Asymmetric Propargylic Amination of Propargylic Carbonates Bearing an Internal Alkyne Group.

We have achieved the nickel-catalyzed asymmetric propargylic amination of propargylic carbonates bearing an internal alkyne group. A wide variety of propargylic carbonates and N-methylaniline derivatives were tolerated under the reaction conditions, providing the corresponding chiral propargylic amines in up to 97% yield with up to 97% ee.