The author describes perspectives gained over many years of engagement in the field of organic electrochemistry. The manuscript will hopefully dispel a number of misconceptions and provide a ...framework for thinking about how electrochemistry can be uniquely applied to solving problems in synthesis and to obtaining mechanistic insights.
The dominant paradigm for inference in psychology is a null-hypothesis significance testing one. Recently, the foundations of this paradigm have been shaken by several notable replication failures. ...One recommendation to remedy the replication crisis is to collect larger samples of participants. We argue that this recommendation misses a critical point, which is that increasing sample size will not remedy psychology’s lack of strong measurement, lack of strong theories and models, and lack of effective experimental control over error variance. In contrast, there is a long history of research in psychology employing small-
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designs that treats the individual participant as the replication unit, which addresses each of these failings, and which produces results that are robust and readily replicated. We illustrate the properties of small-
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and large-
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designs using a simulated paradigm investigating the stage structure of response times. Our simulations highlight the high power and inferential validity of the small-
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design, in contrast to the lower power and inferential indeterminacy of the large-
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design. We argue that, if psychology is to be a mature quantitative science, then its primary theoretical aim should be to investigate systematic, functional relationships as they are manifested at the individual participant level and that, wherever possible, it should use methods that are optimized to identify relationships of this kind.
The nature of the COVID-19 pandemic may require governments to use privacy-encroaching technologies to help contain its spread. One technology involves co-location tracking through mobile Wi-Fi, GPS, ...and Bluetooth to permit health agencies to monitor people's contact with each other, thereby triggering targeted social-distancing when a person turns out to be infected. The effectiveness of tracking relies on the willingness of the population to support such privacy encroaching measures. We report the results of two large surveys in the United Kingdom, conducted during the peak of the pandemic, that probe people's attitudes towards various tracking technologies. The results show that by and large there is widespread acceptance for co-location tracking. Acceptance increases when the measures are explicitly time-limited and come with opt-out clauses or other assurances of privacy. Another possible future technology to control the pandemic involves "immunity passports", which could be issued to people who carry antibodies for the COVID-19 virus, potentially implying that they are immune and therefore unable to spread the virus to other people. Immunity passports have been considered as a potential future step to manage the pandemic. We probe people's attitudes towards immunity passports and find considerable support overall, although around 20% of the public strongly oppose passports.
In response to the COVID-19 pandemic, many Governments are instituting mobile tracking technologies to perform rapid contact tracing. However, these technologies are only effective if the public is ...willing to use them, implying that their perceived public health benefits must outweigh personal concerns over privacy and security. The Australian federal government recently launched the 'COVIDSafe' app, designed to anonymously register nearby contacts. If a contact later identifies as infected with COVID-19, health department officials can rapidly followup with their registered contacts to stop the virus' spread. The current study assessed attitudes towards three tracking technologies (telecommunication network tracking, a government app, and Apple and Google's Bluetooth exposure notification system) in two representative samples of the Australian public prior to the launch of COVIDSafe. We compared these attitudes to usage of the COVIDSafe app after its launch in a further two representative samples of the Australian public. Using Bayesian methods, we find widespread acceptance for all tracking technologies, however, observe a large intention-behaviour gap between people's stated attitudes and actual uptake of the COVIDSafe app. We consider the policy implications of these results for Australia and the world at large.
Protein aggregation causes α-synuclein to switch from its physiological role to a pathological toxic gain of function. Under physiological conditions, monomeric α-synuclein improves ATP synthase ...efficiency. Here, we report that aggregation of monomers generates beta sheet-rich oligomers that localise to the mitochondria in close proximity to several mitochondrial proteins including ATP synthase. Oligomeric α-synuclein impairs complex I-dependent respiration. Oligomers induce selective oxidation of the ATP synthase beta subunit and mitochondrial lipid peroxidation. These oxidation events increase the probability of permeability transition pore (PTP) opening, triggering mitochondrial swelling, and ultimately cell death. Notably, inhibition of oligomer-induced oxidation prevents the pathological induction of PTP. Inducible pluripotent stem cells (iPSC)-derived neurons bearing SNCA triplication, generate α-synuclein aggregates that interact with the ATP synthase and induce PTP opening, leading to neuronal death. This study shows how the transition of α-synuclein from its monomeric to oligomeric structure alters its functional consequences in Parkinson's disease.
A significant improvement of the properties of redox catalysts based on the triarylimidazole framework can be achieved with a simple structural modification. By linking the ortho-carbons of the ...aromatics positioned at C-4 and C-5, a fused framework is generated, removing the distortion from planarity and enhancing the influence of the substituents on the redox properties. This modification leads not only to a much broader range of available redox potentials for the resulting phenanthro9,10-dimidazoles but also to improved stability of the corresponding radical cation. These concepts were verified with eight new phenanthro9,10-dimidazole derivatives, using cyclic voltammetry and DFT calculations. For this purpose, an optimized and general synthetic route to the desired compounds was developed. An excellent linear correlation of the calculated effective ionization potentials with the experimental oxidation potentials was obtained, allowing for an accurate prediction of oxidation potentials of derivatives yet to be synthesized. Moreover, high catalytic activity was found for electro-oxidative C-H activation reactions.
The injection (or removal) of electrons into (or from) a substrate by an electrode can effectively catalyze various redox‐neutral reactions that otherwise require harsh conditions and/or the use of ...reagents. Such processes involve the electrogeneration of an ionic or radical ionic species, which after a coupled chemical step either undergoes a backward electron exchange with the electrode (ECEb mechanism) or triggers a chain process in the bulk solution. Under these circumstances, sub‐stoichiometric amounts of charge are sufficient to achieve a full conversion and conceptionally, the electrons and holes can be understood as being catalysts. This principle has been successfully applied to accomplish a number of redox‐neutral transformations such as molecular rearrangements, Diels‐Alder‐type cycloadditions and radical substitution reactions (SRN1) in a mild and atom‐economical fashion. Although examples have been reported but sporadically since the early 1970s, a number of exciting recent developments have led us to review and discuss these cases using unifying mechanistic concepts that are described herein.
Role reversal: To most electrochemists, the term ‘electrocatalysis’ is known as the facilitation of a heterogeneous electron transfer by a chemical interaction between the electrode and a substrate. The opposite case, the utilization of a heterogeneous electron exchange to catalyze a chemical reaction, is a much less known but yet a very powerful approach in electrosynthesis. This remarkable strategy has been applied to a number of organic reactions and the goal of this Minireview is to discuss these cases using unifying mechanistic concepts.
The feeling of insight in problem solving is typically associated with the sudden realization of a solution that appears obviously correct (Kounios et al., 2006). Salvi et al. (2016) found that a ...solution accompanied with sudden insight is more likely to be correct than a problem solved through conscious and incremental steps. However, Metcalfe (1986) indicated that participants would often present an inelegant but plausible (wrong) answer as correct with a high feeling of warmth (a subjective measure of closeness to solution). This discrepancy may be due to the use of different tasks or due to different methods in the measurement of insight (i.e., using a binary vs. continuous scale). In three experiments, we investigated both findings, using many different problem tasks (e.g., Compound Remote Associates, so-called classic insight problems, and non-insight problems). Participants rated insight-related affect (feelings of Aha-experience, confidence, surprise, impasse, and pleasure) on continuous scales. As expected we found that, for problems designed to elicit insight, correct solutions elicited higher proportions of reported insight in the solution compared to non-insight solutions; further, correct solutions elicited stronger feelings of insight compared to incorrect solutions.
The 'nervous nineties' is a well-known cricket colloquialism that implies that batting within reach of 100 runs is mentally demanding. Despite common acceptance of this phenomenon, no study has used ...a historical test cricket dataset to examine how batting behaviour and performance changes on approach to a century. Accordingly, we explored opensource ball-by-ball data from 712 test cricket matches played between 2004 and 2022 to model the regression discontinuity of batting performance metrics either side of 100 runs. Models were fit using multi-level regression, adjusted for the clustering of balls within players (and where possible, the clustering of matches and innings within players). The analysis revealed that runs per ball and the probability of scoring a boundary increased as batters approached 100 runs. This was followed by a decline of -0.18 runs per ball (95% CI -0.22 to -0.14) and a three-percentage point decline (95% CI 2.2 to 3.8) in the probability of a boundary once a batter reached 100. The modelling revealed no evidence of a change in the probability of a dismissal before and after 100. Our results suggest many batters cope effectively with the psychological demands of playing through the nineties, including by batting aggressively and/or opportunistically to swiftly reach the milestone.
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