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  1. There is considerable interest in MnOH x moieties, particularly in the stepwise changes in those O–H bonds in tandem with Mn oxidation state changes. The reactivity of aquo-derived ligands, {MOH x }, is also heavily influenced by the electronic character of the other ligands. Despite the prevalence of oxygen coordination in biological systems, preparation of mononuclear Mn complexes of this type with all O-donors is rare. Herein, we report several Mn complexes with perfluoropinacolate (pin F ) 2− including the first example of a crystallographically characterized mononuclear {Mn( iii )OH} with all O-donors, K 2 [Mn(OH)(pin F ) 2 ], 3. Complex 3 is prepared via deprotonation of K[Mn(OH 2 )(pin F ) 2 ], 1, the p K a of which is estimated to be 18.3 ± 0.3. Cyclic voltammetry reveals quasi-reversible redox behavior for both 1 and 3 with an unusually large Δ E p , assigned to the Mn( iii / ii ) couple. Using the Bordwell method, the bond dissociation free energy (BDFE) of the O–H bond in {Mn( ii )–OH 2 } is estimated to be 67–70 kcal mol −1 . Complex 3 abstracts H-atoms from 1,2-diphenylhydrazine, 2,4,6-TTBP, and TEMPOH, the latter of which supports a PCET mechanism. Under basic conditions in air, the synthesis of 1 results in K 2 [Mn(OAc)(pin F ) 2 ], 2, proposed to result from the oxidation of Et 2 O to EtOAc by a reactive Mn species, followed by ester hydrolysis. Complex 3 alone does not react with Et 2 O, but addition of O 2 at low temperature effects the formation of a new chromophore proposed to be a Mn( iv ) species. The related complexes K(18C6)[Mn( iii )(pin F ) 2 ], 4, and (Me 4 N) 2 [Mn( ii )(pin F ) 2 ], 5, have also been prepared and their properties discussed in relation to complexes 1–3. 
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    Free, publicly-accessible full text available July 12, 2024
  2. Free, publicly-accessible full text available June 26, 2024
  3. Mitrovic, Antonija ; Bosch, Nigel (Ed.)
    In collaborative problem solving (CPS), people's actions are interactive, interdependent, and temporal. However, it is unclear how actions temporally relate to each other and what are the temporal similarities and differences between successful vs. unsuccessful CPS processes. As such, we apply a temporal analysis approach, Multilevel Vector Autoregression (mlVAR) to investigate CPS processes. Our data were collected from college students who collaborated in triads via a video-conferencing tool (Zoom) to collaborately engage a physics learning game. Video recordings of their verbal interactions were transcribed, coded using a validated CPS framework, and organized into sequences of 10-second windows. Then, mlVAR was applied to the successful vs. unsuccessful CPS sequences to build temporal models for each. A comparison of the models together with a qualitative analysis of the transcripts revealed six temporal relationships common to both, six unique to successful level attempts, and another eight unique to unsuccessful level attempts only. Generally, for successful outcomes, people were likely to answer clarification questions with reasons and to ask for suggestions according to the current game situation, while for unsuccessful CPS level attempts, people were more likely to struggle with unclear instructions and to respond to inappropriate ideas. Overall, our results suggest that mlVAR is an effective approach for temporal analyses of CPS processes by identifying relationships that go beyond a coding and counting approach. 
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  4. Abstract

    Somatic mosaicism is defined as an occurrence of two or more populations of cells having genomic sequences differing at given loci in an individual who is derived from a single zygote. It is a characteristic of multicellular organisms that plays a crucial role in normal development and disease. To study the nature and extent of somatic mosaicism in autism spectrum disorder, bipolar disorder, focal cortical dysplasia, schizophrenia, and Tourette syndrome, a multi-institutional consortium called the Brain Somatic Mosaicism Network (BSMN) was formed through the National Institute of Mental Health (NIMH). In addition to genomic data of affected and neurotypical brains, the BSMN also developed and validated a best practices somatic single nucleotide variant calling workflow through the analysis of reference brain tissue. These resources, which include >400 terabytes of data from 1087 subjects, are now available to the research community via the NIMH Data Archive (NDA) and are described here.

     
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  5. null (Ed.)
    Pyramid evaluation was developed to assess the content of paragraph length summaries of source texts. A pyramid lists the distinct units of content found in several reference summaries, weights content units by how many reference summaries they occur in, and produces three scores based on the weighted content of new summaries. We present an automated method that is more efficient, more transparent, and more complete than previous automated pyramid methods. It is tested on a new dataset of student summaries, and historical NIST data from extractive summarizers. 
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