bluuebunny/crossref_metadata_2025_split huggingface dataset:
N−H and C−H Functionalization of Sulfoximine: Recent Advancement and Prospects
Authors: Ghosh Prasanjit , Ganguly Bhaskar , Das Sajal 
Published: August 2020

AbstractSulfoximine and its congeners are a versatile class of structural motifs widely found in a plethora of pharmaceutical compounds and crop protection industries due to their fascinating structural architecture. Former discoveries nicely demonstrates the synthetic routes of unmasked and various N‐functionalized sulfoximines but recent efforts from the synthetic community have divulged the applicability of sulfoximine analogue as reusable and transformable DG (directing group) to fabricate multifunctionalized (Het)arenes and enhance the bioactivities. Considering the synthetic potentiality and great influence of this scaffold, we provide a summary of N−H/C−H functionalization strategies of sulfoximine and application (as a directing group) with special emphasis on the mechanistic underpinnings. Additionally, we also hoped that this comprehensive review article (up to midst of 2020) will be useful for synthetic researchers and medicinal chemists and will inspire for further novel chemical transformations in this arena.
Pd‐Catalyzed Cross‐Dehydrogenative Coupling of 3‐Benzoyl Substituted Coumarins: Efficient Access to Indeno[2,1‐c]chromene‐6,7‐diones
Authors: Yang Ting , Ding Xingxing , Zhan Xuecheng , Weng Yiyi 
Published: August 2020

AbstractPalladium‐catalyzed cross‐dehydrogenative coupling of 3‐benzoyl substituted coumarins through C−H activation is described to synthesize indeno[2,1‐c]chromene‐6,7‐diones. A broad range of indeno[2,1‐c]chromene‐6,7‐diones using this method could be easily achieved in moderate to good yields (up to 93%).
Big data and poverty governance under Australia and Aotearoa/New Zealand's “social investment” policies
Authors: Staines Zoe , Moore Charlotte , Marston Greg , Humpage Louise 
Published: August 2020

AbstractSurveillance and governance of the poor have been key foci for the critical social policy literature for some time, although scholarship regarding the role of big data in social policy – and how this might differ from previous forms of surveillance – is continuing to emerge. This article contributes to this literature by exploring the use of big data under Australia and Aotearoa/New Zealand's social investment approaches. Both seek to replace social policy spending with “investment” expected to produce future fiscal returns; in the words of a former Aotearoa/New Zealand Prime Minister, they aim to do “more with less”. We argue that big data often provides a poor evidence base for social investment and can, instead, be better understood as part of a panoptic toolkit for poverty governance, mediating continuous surveillance, examination and normalisation of the body politic by enabling the discursive (re)construction of people's identities and subjectivities. This construction serves to exacerbate social inequalities and undermine the rights of ordinary citizens.
Metal‐Templated Design of Chemically Switchable Protein Assemblies with High‐Affinity Coordination Sites
Authors: Kakkis Albert , Gagnon Derek , Esselborn Julian , Britt R. David , Tezcan F. Akif 
Published: August 2020

AbstractTo mimic a hypothetical pathway for protein evolution, we previously tailored a monomeric protein (cyt cb562) for metal‐mediated self‐assembly, followed by re‐design of the resulting oligomers for enhanced stability and metal‐based functions. We show that a single hydrophobic mutation on the cyt cb562surface drastically alters the outcome of metal‐directed oligomerization to yield a new trimeric architecture, (TriCyt1)3.This nascent trimer was redesigned into second and third‐generation variants (TriCyt2)3and (TriCyt3)3with increased structural stability and preorganization for metal coordination. The three TriCyt variants combined furnish a unique platform to 1) provide tunable coupling between protein quaternary structure and metal coordination, 2) enable the construction of metal/pH‐switchable protein oligomerization motifs, and 3) generate a robust metal coordination site that can coordinate all mid‐to‐late first‐row transition‐metal ions with high affinity.
Redox‐Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C−H Di‐ and Trifluoromethoxylation
Authors: Lee Johnny W. , Lim Sanghyun , Maienshein Daniel N. , Liu Peng , Ngai Ming‐Yu 
Published: August 2020

AbstractApplications of TEMPO.catalysis for the development of redox‐neutral transformations are rare. Reported here is the first TEMPO.‐catalyzed, redox‐neutral C−H di‐ and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional‐group tolerance, and can be employed for the late‐stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO./TEMPO+redox catalytic cycle. Mechanistic studies also suggest that Li2CO3plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox‐neutral TEMPO.catalysis.
The Effect of Functional Groups on the Electrocatalytic Activity of Carbon Nanotubes with Different Wall Numbers toward Carbohydrazide Oxidation Reaction
Authors: Wang Haining , Lv Zhaoqian , Zhang Jin , Xiang Yan , Lu Shanfu 
Published: August 2020

AbstractCarbohydrazide could be applied as fuels for fuel cells to avoid the toxicity of hydrazine. Carbon nanotubes (CNTs) exhibit an improved electrocatalytic activity toward carbohydrazide oxidation reaction than other carbon materials like carbon black or multi‐layer graphene, however, the role of defects and functional groups of CNTs for the reaction is not clear. In this study, the electrocatalytic properties of CNTs toward the carbohydrazide oxidation reaction is investigated, which demonstrate that the content of carboxyl groups is crucial to the catalytic activity. The one with higher carboxyl groups exhibits an improved catalytic activity toward carbohydrazide oxidation reaction. Furthermore, density functional theory calculation reveals that the carboxyl groups could increase the adsorption of carbohydrazide molecules on CNTs, which benefits their catalytic activity.
A New Bias Site for Epigenetic Modifications: How Non‐Canonical GC Base Pairs Favor Mechanochemical Cleavage of DNA
Authors: Semyonov Denis A. , Eltsov Ilia V. , Nechipurenko Yury D. 
Published: August 2020

AbstractProperties of non‐canonical GC base pairs and their relations with mechanochemical cleavage of DNA are analyzed. A hypothesis of the involvement of the transient GC wobble base pairs both in the mechanisms of the mechanochemical cleavage of DNA and epigenetic mechanisms involving of 5‐methylcytosine, is proposed. The hypothesis explains the increase in the frequency of the breaks of the sugar‐phosphate backbone of DNA after cytosines, the asymmetric character of these breaks, and an increase in break frequency in CpG after cytosine methylation. As an alternative hypothesis, probable implication of GC+ Hoogsteen base pairs is considered, which now exemplify the best‐studied non‐canonical GC base pairs in the DNA double helix. Also
see the video abstract here https://youtu.be/EUunVWL0ptw.
Crosstalk between Cell Adhesion Complexes in Regulation of Mechanotransduction
Authors: Zuidema Alba , Wang Wei , Sonnenberg Arnoud 
Published: August 2020

AbstractPhysical forces regulate numerous biological processes during development, physiology, and pathology. Forces between the external environment and intracellular actin cytoskeleton are primarily transmitted through integrin‐containing focal adhesions and cadherin‐containing adherens junctions. Crosstalk between these complexes is well established and modulates the mechanical landscape of the cell. However, integrins and cadherins constitute large families of adhesion receptors and form multiple complexes by interacting with different ligands, adaptor proteins, and cytoskeletal filaments. Recent findings indicate that integrin‐containing hemidesmosomes oppose force transduction and traction force generation by focal adhesions. The cytolinker plectin mediates this crosstalk by coupling intermediate filaments to the actin cytoskeleton. Similarly, cadherins in desmosomes might modulate force generation by adherens junctions. Moreover, mechanotransduction can be influenced by podosomes, clathrin lattices, and tetraspanin‐enriched microdomains. This review discusses mechanotransduction by multiple integrin‐ and cadherin‐based cell adhesion complexes, which together with the associated cytoskeleton form an integrated network that allows cells to sense, process, and respond to their physical environment.
Kinetic modeling of microbial growth, enzyme activity, and gene deletions: An integrated model of β‐glucosidase function in Cellvibrio japonicus
Authors: Hwang Jeanice , Hari Archana , Cheng Raymond , Gardner Jeffrey G. , Lobo Daniel 
Published: August 2020

AbstractUnderstanding the complex growth and metabolic dynamics in microorganisms requires advanced kinetic models containing both metabolic reactions and enzymatic regulation to predict phenotypic behaviors under different conditions and perturbations. Most current kinetic models lack gene expression dynamics and are separately calibrated to distinct media, which consequently makes them unable to account for genetic perturbations or multiple substrates. This challenge limits our ability to gain a comprehensive understanding of microbial processes towards advanced metabolic optimizations that are desired for many biotechnology applications. Here, we present an integrated computational and experimental approach for the development and optimization of mechanistic kinetic models for microbial growth and metabolic and enzymatic dynamics. Our approach integrates growth dynamics, gene expression, protein secretion, and gene‐deletion phenotypes. We applied this methodology to build a dynamic model of the growth kinetics in batch culture of the bacterium Cellvibrio japonicus grown using either cellobiose or glucose media. The model parameters were inferred from an experimental data set using an evolutionary computation method. The resulting model was able to explain the growth dynamics of C. japonicus using either cellobiose or glucose media and was also able to accurately predict the metabolite concentrations in the wild‐type strain as well as in β‐glucosidase gene deletion mutant strains. We validated the model by correctly predicting the non‐diauxic growth and metabolite consumptions of the wild‐type strain in a mixed medium containing both cellobiose and glucose, made further predictions of mutant strains growth phenotypes when using cellobiose and glucose media, and demonstrated the utility of the model for designing industrially‐useful strains. Importantly, the model is able to explain the role of the different β‐glucosidases and their behavior under genetic perturbations. This integrated approach can be extended to other metabolic pathways to produce mechanistic models for the comprehensive understanding of enzymatic functions in multiple substrates.
Exploring neural and peripheral physiological correlates of simulator sickness
Authors: Tauscher Jan‐Philipp , Witt Alexandra , Bosse Sebastian , Schottky Fabian W. , Grogorick Steve , Castillo Susana , Magnor Marcus 
Published: August 2020

AbstractThis article investigates neural and physiological correlates of simulator sickness (SS) through a controlled experiment conducted within a fully immersive dome projection system. Our goal is to establish a reliable, objective, and in situ measurable predictive indicator of SS. SS is a problem common to all types of visual simulators consisting of motion sickness‐like symptoms that may be experienced while and after being exposed to a dynamic, immersive visualization. It leads to ethical concerns and impaired validity of simulator‐based research. Due to the popularity of virtual reality devices, the number of people exposed to this problem is increasing and, therefore, it is crucial to find reliable predictors of this condition before any symptoms appear. Despite its relevance and the several theories about its origins, SS cannot yet be quantitatively modeled and predicted. Our results indicate that, while neural correlates did not materialize, physiological measures may be a solid early indicator of oncoming SS.
Conservative approach for management of fractured maxillary central incisors in young adults
Authors: Tinoco Jose Villalobos , Jurado Carlos Alberto , Sayed Mohammed E. , Garcia Cortes Jose Obed , Kaleinikova Zinaida , Hernandez Alfredo , Alshabib Abdulrahman , Tsujimoto Akimasa 
Published: August 2020

AbstractCeramic restorations could be an acceptable treatment choice for fractured central incisors. A successful esthetic and conservative result to restore damaged anterior teeth can be obtained through proper evaluation, diagnostic wax‐up, guided minimal preparations, ceramic selection, and bonding protocols. Handcrafted glass‐based restorations can mimic contours and shape of natural teeth.
Stable High‐Pressure Methane Dry Reforming Under Excess of CO2
Authors: Ramirez Adrian , Lee Kunho , Harale Aadesh , Gevers Lieven , Telalovic Selvedin , Al Solami Bandar , Gascon Jorge 
Published: August 2020

AbstractDry reforming of methane (DRM), the conversion of carbon dioxide and methane into syngas, offers great promise for the recycling of CO2. However, fast catalyst deactivation, especially at the industrially required high pressure, still hampers this process. Here we present a comprehensive study of DRM operation at high pressure (7–28 bars). Our results demonstrate that, under equimolar CH4 : CO2 mixtures, coke formation is unavoidable at high pressures for all catalysts under study. However, under substoichiometric CH4 : CO2 ratios (1 : 3), a stable high pressure operation can be achieved for most catalysts with no sign of deactivation for at least 60 hours at 14 bars, 800 °C and 7500 h−1. In addition to the enhanced stability, under these conditions, the amount of CO2 abated per mol of CH4 fed increases by a 50 %.
Direct Observation of Dynamic Interactions between Orientation‐Controlled Nucleosomes in a DNA Origami Frame
Authors: Feng Yihong , Hashiya Fumitaka , Hidaka Kumi , Sugiyama Hiroshi , Endo Masayuki 
Published: August 2020

AbstractThe nucleosome is one of the most fundamental units involved in gene expression and consequent cell development, differentiation, and expression of cell functions. We report here a method to place reconstituted nucleosomes into a DNA origami frame for direct observation using high‐speed atomic‐force microscopy (HS‐AFM). By using this method, multiple nucleosomes can be incorporated into a DNA origami frame and real‐time movement of nucleosomes can be visualized. The arrangement and conformation of nucleosomes and the distance between two nucleosomes can be designed and controlled. In addition, four nucleosomes can be placed in a DNA frame. Multiple nucleosomes were well accessible in each conformation. Dynamic movement of the individual nucleosomes were precisely monitored in the DNA frame, and their assembly and interaction were directly observed. Neither mica surface modification nor chemical fixation of nucleosomes is used in this method, meaning that the DNA frame not only holds nucleosomes, but also retains their natural state. This method offers a promising platform for investigating nucleosome interactions and for studying chromatin structure.
The Synthesis and Mechanistic Considerations of a Series of Ammonium Monosubstituted H‐Phosphonate Salts
Authors: Lee Keng Lung , Feld Joey , Hume Paul , Söhnel Tilo , Leitao Erin 
Published: August 2020

AbstractA series of ammonium monosubstituted H‐phosphonate salts were synthesized by combining H‐phosphonate diesters with amines in the absence of solvent at 80 °C. Variation of the ester substituent and amine produced a range of ionic liquids with low melting points. The products and by‐products were analyzed by spectroscopic and spectrometric techniques in order to get a better mechanistic picture of the dealkylation and formal dearylation observed. For dialkyl H‐phosphonate diesters, (RO)2P(O)H (R=alkyl), the reaction proceeds via direct dealkylation with the reactivity increasing in the order R=iPr<Et<Me corresponding to DFT calculated activation enthalpies of 22.6, 20.8, and 17.9 kcal mol−1. For the diphenyl H‐phosphonate diesters, (PhO)2P(O)H, the dearylation was found to proceed via phenol‐assisted formation of a 5‐coordinate intermediate, (PhO)3PH(OH), from which P(OPh)3 and water were eliminated. The presence of an equivalent of water then facilitated the formation of P(OH)2OPh and the amine, R'NH2, subsequently abstracted a proton from it to yield [(PhO)PH(O)O]‐[R'NH3]+.
Smart Shell‐by‐Shell Nanoparticles with Tunable Perylene Fluorescence in the Organic Interlayer
Authors: Stiegler Lisa M. S. , Klein Stefanie , Kryschi Carola , Neuhuber Winfried , Hirsch Andreas 
Published: August 2020

AbstractA new series of shell‐by‐shell (SbS)‐functionalized Al2O3 nanoparticles (NPs) containing a perylene core in the organic interlayer as a fluorescence marker is introduced. Initially, the NPs were functionalized with both, a fluorescent perylene phosphonic acid derivative, together with the lipophilic hexadecylphosphonic acid or the fluorophilic (1 H,1 H,2 H,2H‐perfluorodecyl)phosphonic acid. The lipophilic first‐shell functionalized NPs were further implemented with amphiphiles built of aliphatic chains and polar head‐groups. However, the fluorophilic NPs were combined with amphiphiles consisting of fluorocarbon tails and polar head‐groups. Depending on the nature of the combined phosphonic acids and the amphiphiles, tuning of the perylene fluorescence can be accomplished due variations of supramolecular organization with the shell interface. Because the SbS‐functionalized NPs dispose excellent dispersibility in water and in biological media, two sorts of NPs with different surface properties were tested with respect to biological fluorescent imaging applications. Depending on the agglomeration of the NPs, the cellular uptake differs. The uptake of larger agglomerates is facilitated by endocytosis, whereas individualized NPs cross directly the cellular membrane. Also, the larger agglomerates were preferentially incorporated by all tested cells.
Canakinumab to reduce deterioration of cardiac and respiratory function in SARS‐CoV‐2 associated myocardial injury with heightened inflammation (canakinumab in Covid‐19 cardiac injury: The three C study)
Authors: Sheng Calvin C , Sahoo Debasis , Dugar Siddharth , Prada Robier Aguillon , Wang Tom Kai Ming , Abou Hassan Ossama K , Brennan Danielle , Culver Daniel A , Rajendram Prabalini , Duggal Abhijit , Lincoff A Michael , Nissen Steven E , Menon Venu , Cremer Paul C 
Published: August 2020

AbstractBackgroundIn patients with Covid‐19, myocardial injury and increased inflammation are associated with morbidity and mortality. We designed a proof‐of‐concept randomized controlled trial to evaluate whether treatment with canakinumab prevents progressive respiratory failure and worsening cardiac dysfunction in patients with SARS‐CoV2 infection, myocardial injury, and high levels of inflammation.HypothesisThe primary hypothesis is that canakiumab will shorten time to recovery.MethodsThe three C study (canakinumab in Covid‐19 Cardiac Injury, NCT04365153) is a double‐blind, randomized controlled trial comparing canakinumab 300 mg IV, 600 mg IV, or placebo in a 1:1:1 ratio in hospitalized Covid‐19 patients with elevations in troponin and C‐reactive protein (CRP). The primary endpoint is defined as the time in days from randomization to either an improvement of two points on a seven category ordinal scale or discharge from the hospital, whichever occurs first up to 14 days postrandomization. The secondary endpoint is mortality at day 28. A total of 45 patients will be enrolled with an anticipated 5 month follow up period.ResultsBaseline characteristics for the first 20 randomized patients reveal a predominantly male (75%), elderly population (median 67 years) with a high prevalence of hypertension (80%) and hyperlipidemia (75%). CRPs have been markedly elevated (median 16.2 mg/dL) with modest elevations in high‐sensitivity troponin T (median 21 ng/L), in keeping with the concept of enrolling patients with early myocardial injury.ConclusionsThe three C study will provide insights regarding whether IL‐1β inhibition may improve outcomes in patients with SARS‐CoV2 associated myocardial injury and increased inflammation.
Single‐session Comprehend, Cope, and Connect intervention in acute and crisis psychology: A feasibility and acceptability study
Authors: Bullock Jonathan , Whiteley Christopher , Moakes Kaylee , Clarke Isabel , Riches Simon 
Published: August 2020

AbstractComprehend, Cope, and Connect (CCC) is a third‐wave cognitive behavioural approach developed for acute mental health services. The aim of this study was to assess feasibility and acceptability of a newly developed, manualized single‐session CCC intervention delivered face‐to‐face with service users in acute and crisis psychology services in South London. The study adopted a within‐subjects pre‐post‐test design. Participants (N = 23) were recruited from five acute psychiatric wards and a crisis resolution home treatment team. Service users had a range of diagnoses of complex and severe mental health conditions, in particular mood, personality, and psychotic disorders. Feasibility data were gathered for number of times the CCC formulation was accepted, duration of CCC intervention, clinician adherence to manualised protocol, and frequency of goal‐based activity completion. Acceptability data on pre‐ and post‐CCC mood and post‐CCC helpfulness were self‐reported by participants. Findings indicated a significant increase in positive mood (large effect) and moderate–high helpfulness rating postintervention. Most participants reported goal‐based activity completion. There was high fidelity to the protocol, high percentage of acceptance of the formulation and formulation components completed, and frequent single‐session completion. Single‐session CCC appears feasible and acceptable in acute and crisis psychology services and yields formulation‐driven goal‐based activities intended to stabilize mental health crisis. High fidelity to formulation protocol suggests broader applications for single‐session CCC, for example, to support clinical staff to manage crisis situations in their work environment or to train nonpsychologist clinicians to deliver the intervention for service users. A randomized controlled trial of single‐session CCC would increase validity and generalisability of findings.