Interfacing High-Throughput Electrosynthesis and Mass Spectrometric Analysis of Azines.

Combinatorial electrochemistry has great promise for accelerated reaction screening, organic synthesis, and catalysis. Recently, we described a new high-throughput electrochemistry platform, colloquially named "Legion". Legion fits the footprint of a 96-well microtiter plate with simultaneous individual control over all 96 electrochemical cells. Here, we demonstrate the versatility of Legion when coupled with high-throughput mass spectrometry (MS) for electrosynthetic product screening and quantitation. Electrosynthesis of benzophenone azine was selected as a model reaction and was arrayed and optimized using a combination of Legion and nanoelectrospray ionization MS. The combination of high-throughput synthesis with Legion and analysis via MS proves a compelling strategy for accelerating reaction discovery and optimization in electro-organic synthesis.

Brachial Plexus Nerve Injuries and Disorders: MR Imaging-Ultrasound Correlation.

Multimodality imaging of the brachial plexus is essential to accurately localize the lesion and characterize the pathology and site of injury. A combination of computed tomography (CT), ultrasound, and MR imaging is useful along with clinical and nerve conduction studies. Ultrasound and MR imaging in combination are effective to accurately localize the pathology in most of the cases. Accurate reporting of the pathology with dedicated MR imaging protocols in conjunction with Doppler ultrasound and dynamic imaging provides practical and useful information to help the referring physicians and surgeons to optimize medical or surgical treatment regimens.

Migration of Hydride, Methyl, and Chloride Ligands between Al and M in (PAlP)M Pincer Complexes (M = Rh or Ir).

Protolysis of AlMe3 or AlBui3 with 2-diisopropylphosphinopyrrole (1) yields molecules containing two flanking phosphines and a central Al-Me (2-Me), Al-iBu (2-iBu), or Al-H (2-H) unit. The reactions of 2-Me with [L2MCl]2 (L = cyclooctene or 1/2 1,5-cyclooctadiene and M = Rh or Ir) in the presence of pyridine produces PAlClP pincer complexes (3-Rh and 3-Ir) with Al-Cl and M-Me bonds. The analogous reaction of a mixture of 2-iBu and 2-H with [L2MCl]2 and pyridine resulted in the formation of analogous Rh-H (4-Rh) and Ir-H (4-Ir) complexes. Treatment of 3-Rh with NaBEt3H produced compound 5-Rh with an Al-Me and a Rh-H bond; the analogous reaction of 3-Ir did not result in a clean product. 4-Ir accepted an equivalent of H2 to produce 6-Ir with two terminal Ir-H bonds and one bridging Al-H-Ir moiety, whereas 4-Rh did not react with H2. The density functional theoretical treatment is in accord with this finding, highlights the likely mechanism for the H2 addition, and supports the bonding picture in 6-Ir arising from NMR and X-ray diffraction (XRD) observations. Spectroscopic data and XRD studies are consistent with distorted square-pyramidal structures (about Rh or Ir) for compounds 3-5, with an alane occupying the apical position. Complexes 3 and 4 possess some of the shortest known Rh-Al or Ir-Al distances.

Distinct modes of Si-H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand.

Syntheses of Rh complexes of the phosphine-amido-silane SiNP ligand are reported. The reaction of the parent (SiNP)H ligand (4) with 0.5 equiv. [(COE)RhCl]2 (COE = cis-cyclooctene) in the presence of NaN(SiME3)2 resulted in the formation of (SiNP)Rh(COE) (5). Compound 5 was converted to a series of (SiNP)Rh(P(OR)3) complexes 6-10 (R = Ph, iPr, nBu, Et, or Me) by treatment with the corresponding phosphite. NMR and XRD structural data, as well as the DFT computational analysis indicate that compounds 5-10 are divided into two structural Types (A and B), differing in the nature of the interaction of the Si-H bond of the SiNP ligand with Rh.

The perceptions of social media users of digital detox apps considering personality traits.

The purpose of this study was to investigate the perceptions of users about using digital detox applications and to display relationships among personality traits and technology-related variables. This study was designed using survey approach and employed Generalized Structured Component Analysis (GSCA). As such, 11 hypotheses were constructed and tested. The study recruited 263 participants who utilize detox applications to avoid social media distractions. Data were collected through Google Form and analyzed using GSCA Pro 1.1 to better understand whether the proposed conceptual model fits the data. The results of the study indicated that behavioral intention predicted usage behavior significantly; performance expectancy, effort expectancy, and social influence positively affected behavioral intention; in turn, agreeableness and extroversion positively influenced performance expectancy, and extroversion affected effort expectancy; finally, neuroticism had a statistically significant and negatively associated with effort expectancy of using social media detox apps. The significant exceptions were that facilitating conditions were not predictive of behavioral intention, openness to experience did not influence performance expectancy, and conscientiousness was not linked to effort expectancy. The proposed conceptual model explained 56.68% of the amount of variation, indicating that instructors, policy makers and software designers should consider personal factors for preparing practical intervention approaches to mitigate learning issues related to social media distraction.

Examining data visualization pitfalls in scientific publications.

Data visualization blends art and science to convey stories from data via graphical representations. Considering different problems, applications, requirements, and design goals, it is challenging to combine these two components at their full force. While the art component involves creating visually appealing and easily interpreted graphics for users, the science component requires accurate representations of a large amount of input data. With a lack of the science component, visualization cannot serve its role of creating correct representations of the actual data, thus leading to wrong perception, interpretation, and decision. It might be even worse if incorrect visual representations were intentionally produced to deceive the viewers. To address common pitfalls in graphical representations, this paper focuses on identifying and understanding the root causes of misinformation in graphical representations. We reviewed the misleading data visualization examples in the scientific publications collected from indexing databases and then projected them onto the fundamental units of visual communication such as color, shape, size, and spatial orientation. Moreover, a text mining technique was applied to extract practical insights from common visualization pitfalls. Cochran's Q test and McNemar's test were conducted to examine if there is any difference in the proportions of common errors among color, shape, size, and spatial orientation. The findings showed that the pie chart is the most misused graphical representation, and size is the most critical issue. It was also observed that there were statistically significant differences in the proportion of errors among color, shape, size, and spatial orientation.

Insula cortex gates the interplay of action observation and preparation for controlled imitation.

Perceiving, anticipating and responding to the actions of another person are fundamentally entwined processes such that seeing another's movement can prompt automatic imitation, as in social mimicry and contagious yawning. Yet the direct-matching of others' movements is not always appropriate, so this tendency must be controlled. This necessitates the hierarchical integration of the systems for action mirroring with domain-general control networks. Here we use functional magnetic resonance imaging (fMRI) and computational modelling to examine the top-down and context-dependent modulation of mirror representations and their influence on motor planning. Participants performed actions that either intentionally or incidentally imitated, or counter-imitated, an observed action. Analyses of these fMRI data revealed a region in the mid-occipital gyrus (MOG) where activity differed between imitation versus counter-imitation in a manner that depended on whether this was intentional or incidental. To identify broader cortical network mechanisms underlying this interaction between intention and imitativeness, we used dynamic causal modelling to pose specific hypotheses which embody assumptions about inter-areal interactions and contextual modulations. These models each incorporated four regions - medial temporal V5 (early motion perception), MOG (action-observation), supplementary motor area (action planning), and anterior insula (executive control) - but differ in their interactions and hierarchical structure. The best model of our data afforded a crucial role for the anterior insula, gating the interaction of supplementary motor area and MOG activity. This provides a novel brain network-based account of task-dependent control over the integration of motor planning and mirror systems, with mirror responses suppressed for intentional counter-imitation.

Narratives of Undergraduate Research, Mentorship, and Teaching at UCLA.

This work describes select narratives pertaining to undergraduate teaching and mentorship at UCLA Chemistry and Biochemistry by Alex Spokoyny and his junior colleagues. Specifically, we discuss how individual undergraduate researchers contributed and jump-started multiple research themes since the conception of our research laboratory. This work also describes several recent innovations in the inorganic and general chemistry courses taught by Spokoyny at UCLA with a focus of nurturing appreciation for research and creative process in sciences including the use of social media platforms.

Intracranial-EEG evidence for medial temporal pole driving amygdala activity induced by multi-modal emotional stimuli.

The temporal pole (TP) is an associative cortical region required for complex cognitive functions such as social and emotional cognition. However, mapping the TP with functional magnetic resonance imaging is technically challenging and thus understanding its interaction with other key emotional circuitry, such as the amygdala, remains elusive. We exploited the unique advantages of stereo-electroencephalography (sEEG) to assess the responses of the TP and the amygdala during the perception of emotionally salient stimuli of pictures, music and movies. These stimuli consistently elicited high gamma responses (70-140 Hz) in both the TP and the amygdala, accompanied by functional connectivity in the low frequency range (2-12 Hz). Computational analyses suggested that the TP drove this effect in the theta frequency range, modulated by the emotional valence of the stimuli. Notably, cross-frequency analysis indicated the phase of theta oscillations in the TP modulated the amplitude of high gamma activity in the amygdala. These results were reproducible across three types of sensory inputs including naturalistic stimuli. Our results suggest that multimodal emotional stimuli induce a hierarchical influence of the TP over the amygdala.

Effective connectivity of the anterior hippocampus predicts recollection confidence during natural memory retrieval.

Human interactions with the world are influenced by memories of recent events. This effect, often triggered by perceptual cues, occurs naturally and without conscious effort. However, the neuroscience of involuntary memory in a dynamic milieu has received much less attention than the mechanisms of voluntary retrieval with deliberate purpose. Here, we investigate the neural processes driven by naturalistic cues that relate to, and presumably trigger the retrieval of recent experiences. Viewing the continuation of recently viewed clips evokes greater bilateral activation in anterior hippocampus, precuneus and angular gyrus than naïve clips. While these regions manifest reciprocal connectivity, continued viewing specifically modulates the effective connectivity from the anterior hippocampus to the precuneus. The strength of this modulation predicts participants' confidence in later voluntary recall of news details. Our study reveals network mechanisms of dynamic, involuntary memory retrieval and its relevance to metacognition in a rich context resembling everyday life.

Improving the Test-Retest Reliability of Resting State fMRI by Removing the Impact of Sleep.

Resting state functional magnetic resonance imaging (rs-fMRI) provides a powerful tool to examine large-scale neural networks in the human brain and their disturbances in neuropsychiatric disorders. Thanks to its low demand and high tolerance, resting state paradigms can be easily acquired from clinical population. However, due to the unconstrained nature, resting state paradigm is associated with excessive head movement and proneness to sleep. Consequently, the test-retest reliability of rs-fMRI measures is moderate at best, falling short of widespread use in the clinic. Here, we characterized the effect of sleep on the test-retest reliability of rs-fMRI. Using measures of heart rate variability (HRV) derived from simultaneous electrocardiogram (ECG) recording, we identified portions of fMRI data when subjects were more alert or sleepy, and examined their effects on the test-retest reliability of functional connectivity measures. When volumes of sleep were excluded, the reliability of rs-fMRI is significantly improved, and the improvement appears to be general across brain networks. The amount of improvement is robust with the removal of as much as 60% volumes of sleepiness. Therefore, test-retest reliability of rs-fMRI is affected by sleep and could be improved by excluding volumes of sleepiness as indexed by HRV. Our results suggest a novel and practical method to improve test-retest reliability of rs-fMRI measures.

Quantification of free-living activity patterns using accelerometry in adults with mental illness.

Physical activity is disrupted in many psychiatric disorders. Advances in everyday technologies - such as accelerometers in smart phones - opens exciting possibilities for non-intrusive acquisition of activity data. Successful exploitation of this opportunity requires the validation of analytical methods that can capture the full movement spectrum. The study aim was to demonstrate an analytical approach to characterise accelerometer-derived activity patterns. Here, we use statistical methods to characterize accelerometer-derived activity patterns from a heterogeneous sample of 99 community-based adults with mental illnesses. Diagnoses were screened using the Mini International Neuropsychiatric Interview, and participants wore accelerometers for one week. We studied the relative ability of simple (exponential), complex (heavy-tailed), and composite models to explain patterns of activity and inactivity. Activity during wakefulness was a composite of brief random (exponential) movements and complex (heavy-tailed) processes, whereas movement during sleep lacked the heavy-tailed component. In contrast, inactivity followed a heavy-tailed process, lacking the random component. Activity patterns differed in nature between those with a diagnosis of bipolar disorder and a primary psychotic disorder. These results show the potential of complex models to quantify the rich nature of human movement captured by accelerometry during wake and sleep, and the interaction with diagnosis and health.

Blue Phosphorescent Zwitterionic Iridium(III) Complexes Featuring Weakly Coordinating nido-Carborane-Based Ligands.

We report the development of a new class of phosphorescent zwitterionic bis(heteroleptic) Ir(III) compounds containing pyridyl ligands with weakly coordinating nido-carboranyl substituents. Treatment of phenylpyridine-based Ir(III) precursors with C-substituted ortho-carboranylpyridines in 2-ethoxyethanol results in a facile carborane deboronation and the formation of robust and highly luminescent metal complexes. The resulting nido-carboranyl fragments associate with the cationic Ir(III) center through primarily electrostatic interactions. These compounds phosphoresce at blue wavelengths (450-470 nm) both in a poly(methyl methacrylate) (PMMA) matrix and in solution at 77 K. These complexes display structural stability at temperatures beyond 300 °C and quantum yields greater than 40%. Importantly, the observed quantum yields correspond to a dramatic 10-fold enhancement over the previously reported Ir(III) congeners featuring carboranyl-containing ligands in which the boron cluster is covalently attached to the metal. Ultimately, this work suggests that the use of a ligand framework containing a weakly coordinating anionic component can provide a new avenue for designing efficient Ir(III)-based phosphorescent emitters.

A hierarchy of timescales explains distinct effects of local inhibition of primary visual cortex and frontal eye fields.

Within the primate visual system, areas at lower levels of the cortical hierarchy process basic visual features, whereas those at higher levels, such as the frontal eye fields (FEF), are thought to modulate sensory processes via feedback connections. Despite these functional exchanges during perception, there is little shared activity between early and late visual regions at rest. How interactions emerge between regions encompassing distinct levels of the visual hierarchy remains unknown. Here we combined neuroimaging, non-invasive cortical stimulation and computational modelling to characterize changes in functional interactions across widespread neural networks before and after local inhibition of primary visual cortex or FEF. We found that stimulation of early visual cortex selectively increased feedforward interactions with FEF and extrastriate visual areas, whereas identical stimulation of the FEF decreased feedback interactions with early visual areas. Computational modelling suggests that these opposing effects reflect a fast-slow timescale hierarchy from sensory to association areas.

Surface Dipole Control of Liquid Crystal Alignment.

Detailed understanding and control of the intermolecular forces that govern molecular assembly are necessary to engineer structure and function at the nanoscale. Liquid crystal (LC) assembly is exceptionally sensitive to surface properties, capable of transducing nanoscale intermolecular interactions into a macroscopic optical readout. Self-assembled monolayers (SAMs) modify surface interactions and are known to influence LC alignment. Here, we exploit the different dipole magnitudes and orientations of carboranethiol and -dithiol positional isomers to deconvolve the influence of SAM-LC dipolar coupling from variations in molecular geometry, tilt, and order. Director orientations and anchoring energies are measured for LC cells employing various carboranethiol and -dithiol isomer alignment layers. The normal component of the molecular dipole in the SAM, toward or away from the underlying substrate, was found to determine the in-plane LC director orientation relative to the anisotropy axis of the surface. By using LC alignment as a probe of interaction strength, we elucidate the role of dipolar coupling of molecular monolayers to their environment in determining molecular orientations. We apply this understanding to advance the engineering of molecular interactions at the nanoscale.

Network dysfunction of emotional and cognitive processes in those at genetic risk of bipolar disorder.

The emotional and cognitive vulnerabilities that precede the development of bipolar disorder are poorly understood. The inferior frontal gyrus-a key cortical hub for the integration of cognitive and emotional processes-exhibits both structural and functional changes in bipolar disorder, and is also functionally impaired in unaffected first-degree relatives, showing diminished engagement during inhibition of threat-related emotional stimuli. We hypothesized that this functional impairment of the inferior frontal gyrus in those at genetic risk of bipolar disorder reflects the dysfunction of broader network dynamics underlying the coordination of emotion perception and cognitive control. To test this, we studied effective connectivity in functional magnetic resonance imaging data acquired from 41 first-degree relatives of patients with bipolar disorder, 45 matched healthy controls and 55 participants with established bipolar disorder. Dynamic causal modelling was used to model the neuronal interaction between key regions associated with fear perception (the anterior cingulate), inhibition (the left dorsolateral prefrontal cortex) and the region upon which these influences converge, namely the inferior frontal gyrus. Network models that embodied non-linear, hierarchical relationships were the most strongly supported by data from our healthy control and bipolar participants. We observed a marked difference in the hierarchical influence of the anterior cingulate on the effective connectivity from the dorsolateral prefrontal cortex to the inferior frontal gyrus that is unique to the at-risk cohort. Non-specific, non-hierarchical mechanisms appear to compensate for this network disturbance. We thus establish a specific network disturbance suggesting dysfunction in the processes that support hierarchical relationships between emotion and cognitive control in those at high genetic risk for bipolar disorder.

Out-of-sync: disrupted neural activity in emotional circuitry during film viewing in melancholic depression.

While a rich body of research in controlled experiments has established changes in the neural circuitry of emotion in major depressive disorders, little is known as to how such alterations might translate into complex, naturalistic settings--namely involving dynamic multimodal stimuli with rich contexts, such as those provided by films. Neuroimaging paradigms employing dynamic natural stimuli alleviate the anxiety often associated with complex tasks and eschew the need for laboratory-style abstractions, hence providing an ecologically valid means of elucidating neural underpinnings of neuropsychiatric disorders. To probe the neurobiological signature of refined depression subtypes, we acquired functional neuroimaging data in patients with the melancholic subtype of major depressive disorder during free viewing of emotionally salient films. We found a marked disengagement of ventromedial prefrontal cortex during natural viewing of a film with negative emotional valence in patients with melancholia. This effect significantly correlated with depression severity. Such changes occurred on the background of diminished consistency of neural activity in visual and auditory sensory networks, as well as higher-order networks involved in emotion and attention, including bilateral intraparietal sulcus and right anterior insula. These findings may reflect a failure to re-allocate resources and diminished reactivity to external emotional stimuli in melancholia.

Scene unseen: Disrupted neuronal adaptation in melancholia during emotional film viewing.

Impairments in attention and concentration are distinctive features of melancholic depression, and may diminish the ability to shift focus away from internal dysphoric states. Disrupted brain networks may underlie the inability to effectively disengage from interoceptive signals in this disorder. This study investigates changes in effective connectivity between cortical systems supporting attention, interoception, and perception in those with melancholic depression when shifting attention from rest to viewing dynamic film stimuli. We hypothesised that those with melancholia would show impaired attentional shifting from rest to emotional film viewing, captured in neuronal states that differed little across conditions. Functional magnetic resonance imaging (fMRI) data were acquired from 48 participants (16 melancholic depressed, 16 non-melancholic depressed, and 16 healthy controls) at rest and whilst viewing emotionally salient movies. Using independent component analysis, we identified 8 cortical modes (default mode, executive control, left/right frontoparietal attention, left/right insula, visual and auditory) and studied their dynamics using dynamic causal modelling. Engagement with dynamic emotional material diminished in melancholia and was associated with network-wide increases in effective connectivity. Melancholia was also characterised by an increase in effective connectivity amongst cortical regions involved in attention and interoception when shifting from rest to negative film viewing, with the converse pattern in control participants. The observed involvement of attention- and insula-based cortical systems highlights a potential neurobiological mechanism for disrupted attentional resource allocation, particularly in switching between interoceptive and exteroceptive signals, in melancholia.

Reciprocal interactions of the SMA and cingulate cortex sustain premovement activity for voluntary actions.

Voluntary action is one of the core functions of the human brain, and is accompanied by the well known readiness potential or Bereitschaftspotential. A network of cortical areas is responsible for the motor preparation process, including the anterior mid-cingulate cortex (aMCC) and the SMA. However, the relationship between activity in these regions during movement preparation and the readiness potential is poorly understood. We examined this relationship by integrating simultaneously acquired EEG and fMRI through computational modeling. We first observed that global field power of premovement neural activity showed a specific correlation with BOLD responses in the aMCC. We then used dynamic causal modeling to infer premovement interactions between these regions and their relationship to the premovement neural activity underlying the readiness potential. These analyses suggest that SMA and aMCC have strong reciprocal connections that act to sustain each other's activity, and that this interaction is mediated during movement preparation according to the readiness potential amplitude, as reflected in global cortical field power. Our study suggests that the reciprocal connections between SMA and aMCC are important to maintain the sustained activity of the readiness potential before movement and lead to a weak system instability at movement onset. We suggest that the effective connectivity of this network underlies its functional role in the preparation of self-generated actions.