Hydridosilylamido complexes of Ta and Mo isolobal with Berry's zirconocenes: syntheses, β-Si–H agostic interactions, catalytic hydrosilylation, and insight into mechanism

2016 ◽  
Vol 45 (6) ◽  
pp. 2554-2561 ◽  
Author(s):  
Nicolas A. McLeod ◽  
Lyudmila G. Kuzmina ◽  
Ilia Korobkov ◽  
Judith A. K. Howard ◽  
Georgii I. Nikonov

The β-SiH agostic complex (ArN)2Mo{η3-N(tBu)SiMe2–H}H is a pre-catalyst for hydrosilylation of carbonyls. Mechanistic studies revealed a non-hydride mechanism, with the benzoxy complex 8 being the resting state.

2018 ◽  
Vol 39 (01) ◽  
pp. 003-011 ◽  
Author(s):  
Theo Moraes ◽  
Malcolm Sears ◽  
Padmaja Subbarao

AbstractAsthma is a heterogeneous disorder with a complex etiology. Prevalence rates for asthma have been increasing in many countries over the past few decades. While it is unclear why this increase is occurring, the variation reported in asthma prevalence and severity associated with ethnicity offers some insight into the determinants of asthma. In this chapter, we discuss the data linking asthma to ethnicity and some of the factors that may explain this association. These include socioeconomic status, environmental exposures, the host microbiome, and genetics. A better understanding of these processes may inform future mechanistic studies and identify modifiable risk factors for targeted health care interventions.


2015 ◽  
Vol 5 (3) ◽  
pp. 1775-1782 ◽  
Author(s):  
Soumen Kundu ◽  
Arani Chanda ◽  
Jasper V. K. Thompson ◽  
George Diabes ◽  
Sushil K. Khetan ◽  
...  

TAML and H2O2remove toxic nitrophenol pollutants producing innocuous minerals. Mechanistic studies reveal the substrate inhibition due to the reversible binding of nitrophenolate to iron(iii) of the TAML resting state.


2011 ◽  
Vol 23 (12) ◽  
pp. 4022-4037 ◽  
Author(s):  
Angela R. Laird ◽  
P. Mickle Fox ◽  
Simon B. Eickhoff ◽  
Jessica A. Turner ◽  
Kimberly L. Ray ◽  
...  

An increasingly large number of neuroimaging studies have investigated functionally connected networks during rest, providing insight into human brain architecture. Assessment of the functional qualities of resting state networks has been limited by the task-independent state, which results in an inability to relate these networks to specific mental functions. However, it was recently demonstrated that similar brain networks can be extracted from resting state data and data extracted from thousands of task-based neuroimaging experiments archived in the BrainMap database. Here, we present a full functional explication of these intrinsic connectivity networks at a standard low order decomposition using a neuroinformatics approach based on the BrainMap behavioral taxonomy as well as a stratified, data-driven ordering of cognitive processes. Our results serve as a resource for functional interpretations of brain networks in resting state studies and future investigations into mental operations and the tasks that drive them.


2014 ◽  
Vol 12 (36) ◽  
pp. 7059-7067 ◽  
Author(s):  
Nicholas K. Pinkin ◽  
Marcey L. Waters

Iterative monomer redesign leads to a Kme3-peptide receptor with 10-fold tighter affinity and 5-fold improved selectivity over Kme2 than the original receptor. Thermodynamic analysis provides insight into this improvement.


2021 ◽  
Author(s):  
Sii Hong Lau ◽  
Meredith Borden ◽  
Talia Steiman ◽  
Lucy Wang ◽  
Marvin Parasram ◽  
...  

A Ni/photoredox-catalyzed enantioselective reductive coupling of styrene oxides and aryl iodides is reported. This reaction affords access to enantioenriched 2,2-diarylalcohols from racemic epoxides via a stereoconvergent mechanism. Multivariate linear regression (MVLR) analysis with 29 bioxazoline (BiOx) and biimidazoline (BiIm) ligands revealed that enantioselectivity correlates with electronic properties of the ligands, with more electron-donating ligands affording higher ee’s. Mechanistic studies were conducted, lending support to the hypothesis that the electronic character of the ligands influences the enantioselectivity by altering the position of the transition state structure along the reaction coordinate. This study demonstrates the benefits of utilizing statistical modeling as a platform for mechanistic understanding and provides new insight into an emerging class of chiral ligands for stereoconvergent Ni and Ni/photoredox cross-coupling.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Ken-Hsien Su ◽  
Jen-Jui Hsueh ◽  
Tainsong Chen ◽  
Fu-Zen Shaw

AbstractNeurofeedback training (NFT) enables users to learn self-control of EEG activity of interest and then to create many benefits on cognitive function. A considerable number of nonresponders who fail to achieve successful NFT have often been reported in the within-session prediction. This study aimed to investigate successful EEG NFT of upregulation alpha activity in terms of trainability, independence, and between-session predictability validation. Forty-six participants completed 12 training sessions. Spectrotemporal analysis revealed the upregulation success on brain activity of 8–12 Hz exclusively to demonstrate trainability and independence of alpha NFT. Three learning indices of between-session changes exhibited significant correlations with eyes-closed resting state (ECRS) alpha amplitude before the training exclusively. Through a stepwise linear discriminant analysis, the prediction model of ECRS’s alpha frequency band amplitude exhibited the best accuracy (89.1%) validation regarding the learning index of increased alpha amplitude on average. This study performed a systematic analysis on NFT success, the performance of the 3 between-session learning indices, and the validation of ECRS alpha activity for responder prediction. The findings would assist researchers in obtaining insight into the training efficacy of individuals and then attempting to adapt an efficient strategy in NFT success.


2011 ◽  
Vol 23 (12) ◽  
pp. 3841-3854 ◽  
Author(s):  
Joost Wegman ◽  
Gabriele Janzen

Objects along a route can help us to successfully navigate through our surroundings. Previous neuroimaging research has shown that the parahippocampal gyrus (PHG) distinguishes between objects that were previously encountered at navigationally relevant locations (decision points) and irrelevant locations (nondecision points) during simple object recognition. This study aimed at unraveling how this neural marking of objects relevant for navigation is established during learning and postlearning rest. Twenty-four participants were scanned using fMRI while they were viewing a route through a virtual environment. Eye movements were measured, and brain responses were time-locked to viewing each object. The PHG showed increased responses to decision point objects compared with nondecision point objects during route learning. We compared functional connectivity between the PHG and the rest of the brain in a resting state scan postlearning with such a scan prelearning. Results show that functional connectivity between the PHG and the hippocampus is positively related to participants' self-reported navigational ability. On the other hand, connectivity with the caudate nucleus correlated negatively with navigational ability. These results are in line with a distinction between egocentric and allocentric spatial representations in the caudate nucleus and the hippocampus, respectively. Our results thus suggest a relation between navigational ability and a neural preference for a specific type of spatial representation. Together, these results show that the PHG is immediately involved in the encoding of navigationally relevant object information. Furthermore, they provide insight into the neural correlates of individual differences in spatial ability.


2016 ◽  
Vol 138 (16) ◽  
pp. 5380-5391 ◽  
Author(s):  
Justin R. Griffiths ◽  
Jerome B. Keister ◽  
Steven T. Diver

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