bluuebunny/crossref_metadata_2025 huggingface dataset:
Nitroaromatics as High‐Energy Organic Cathode Materials for Rechargeable Alkali‐Ion (Li+, Na+, and K+) Batteries
Authors: Liu Xudong , Ye Zhibin
Published: December 2020

Organic cathode materials with existing redox functionalities are attracting increasing attention for rechargeable alkali‐ion batteries due to their high theoretical gravimetric capacity, molecular diversity, and sustainability. However, they are still restricted in specific capacity and energy density. The discovery of new multielectron redox‐active functionalities that can impart significantly enhanced capacity and energy density is highly desired. Herein, a group of organic nitroaromatic compounds (p‐, o‐, and m‐dinitrobenzene (DNB)) is reported as novel high‐energy cathode materials for alkali‐ion batteries. For the first time, nitro groups in DNBs are found to undergo an electrochemically reversible two‐step two‐phase reaction at a voltage above 2 V, rendering a high theoretical capacity of 638 mAh g−1. A systematic study is undertaken to reveal the reaction mechanism and verify the redox reversibility. By confining the optimum p‐DNB within a microporous carbon nanosphere host, record‐high reversible capacities of 620, 573, and 536 mAh g−1 at 50 mA g−1 are achieved for lithium‐, sodium‐, and potassium‐ion batteries, respectively. Demonstrating nitro as a unique redox‐reversible functionality, this work opens a new direction in the development of novel high‐performance organic nitroaromatic cathode materials for next‐generation alkali‐ion batteries.
Arene diruthenium(II)‐mediated synthesis of imines from alcohols and amines under aerobic condition
Authors: Tamilthendral Veerappan , Ramesh Rengan , Malecki Jan Grzegorz
Published: December 2020

The utility and selectivity of the newly synthesized dinuclear arene Ru(II) complex were demonstrated towards the synthesis of imines from coupling of alcohols and amines in the aerobic condition. Analytical and various spectral methods have been used to establish the unprecedented formation of the new thiolato‐bridged dinuclear ruthenium complex. The molecular structure of the titled complex was evidenced with aid of X‐ray crystallographic technique. A wide range of imines were obtained in good‐to‐excellent yields up to 98% and water as the by‐product through an acceptorless dehydrogenative coupling of alcohols with amines. The catalytic reaction operated a concise atom economical without any oxidant with 1 mol% of the catalyst load. Further, the role of base, solvent and catalyst loading of the coupling reaction has been investigated. A plausible mechanism has been described and was found to proceed via the formation of an aldehyde intermediate. Short synthesis of antibacterial drug N‐(salicylidene)‐2‐hydroxyaniline illustrated the utility of the present protocol.
Amido PNP pincer complexes of palladium(II) and platinum(II): Synthesis, structure, and reactivity
Authors: Huang Mei‐Hui , Lee Wei‐Ying , Zou Xue‐Ru , Lee Chia‐Chin , Hong Sheng‐Bo , Liang Lan‐Chang
Published: December 2020

The synthesis of a series of divalent palladium and platinum complexes containing amido PNP pincer ligands of the type [N(o‐C6H4PR2)2]− (R = Ph (1a), iPr (1b)) is reported. Metathetical reactions of [1a–b]PdCl or [1a–b]PtCl with a variety of alkyl Grignard reagents or LiHBEt3 in ethereal or arene solutions generate their corresponding alkyl or hydride complexes [1a]PdR1 (R1 = Me, Et, nBu), [1b]PdR1 (R1 = Me, Et, H), [1a]PtR1 (R1 = Me, Et, nBu, nHexyl, H), and [1b]PtR1 (R1 = Me, H). Although these organometallic complexes are all thermally stable, including those containing β‐hydrogen atoms even at elevated temperatures, compounds [1a]PdH and [1b]PtR1 (R1 = Et, nBu, nHexyl) are not isolable due to facile decomposition. The stability and reactivity of these complexes are discussed. The chloro [1a]PdCl is a superior catalyst precursor to [1b]PdCl, [1a]PtCl, and [1b]PtCl in Kumada couplings, affording, for instance, n‐butyl arenes nearly quantitatively. The X‐ray structures of [1b]PtCl, [1b]PtMe, [1b]PdEt, [1a]PtnBu, [1b]PdH, and [1b]PtH are presented.
Design and synthesis of novel di‐ and triblock amphiphilic polyelectrolytes: Improving salt‐induced viscosity reduction of water solutions for potential application in enhanced oil recovery
Authors: Boulif Nadia , Sebakhy Khaled O. , Joosten Hidde , Raffa Patrizio
Published: December 2020

In the present study, three different block copolymers based on styrene, tert‐butyl methacrylate, and glycidyl methacrylate (GMA) were synthesized via sequential atom transfer radical polymerization. The addition of the GMA block was found to be best performed at 60°C. The polymers were then hydrolyzed and neutralized, to afford amphiphilic block copolymers, and the rheological properties of their aqueous solutions were measured, in order to investigate solution properties relevant for enhanced oil recovery, as a function of the polymer structure. It was observed that these polymers behave as thickening agents with shear thinning behavior. As expected, the polymers were sensitive to the presence of salt, as lower viscosities were recorded in saline water. However, the viscosity is less affected by high salinity, when compared to previously studied analogous diblock systems. In the best case, the viscosity only decreased by a factor of 1.8 upon salt addition whereas it decreased by a factor of 10 in previously reported non‐GMA containing polymers. Finally, thermo‐responsive behavior was found for one of the synthesized polymers. In particular, a hydrolyzed triblock poly[styrene‐b‐tert‐butyl methacrylate‐b‐glycidyl methacrylate], which synthesis is reported here for the first time, showed a thermothickening behavior, promising for the intended application in oil recovery.
From Diagnosis to Prognosis: Revisiting the Meaning of Muscle ISG15 Overexpression in Juvenile Inflammatory Myopathies
Authors: Hou Cyrielle , Durrleman Chloé , Periou Baptiste , Barnerias Christine , Bodemer Christine , Desguerre Isabelle , Quartier Pierre , Melki Isabelle , Rice Gillian I. , Rodero Mathieu P. , Charuel Jean‐Luc , Relaix Fréderic , Bader‐Meunier Brigitte , Authier FrançoisJérôme , Gitiaux Cyril
Published: December 2020

Objective

Juvenile idiopathic inflammatory/immune myopathies (IIMs) constitute a highly heterogeneous group of disorders with diagnostic difficulties and prognostic uncertainties. Circulating myositis‐specific autoantibodies (MSAs) have been recognized as reliable tools for patient substratification. Considering the key role of type I interferon (IFN) up‐regulation in juvenile IIM, we undertook the present study to investigate whether IFN‐induced 15‐kd protein (ISG‐15) could be a reliable biomarker for stratification and diagnosis and to better elucidate its role in juvenile IIM pathophysiology.

Methods

The study included 56 patients: 24 with juvenile dermatomyositis (DM), 12 with juvenile overlap myositis (OM), 10 with Duchenne muscular dystrophy, and 10 with congenital myopathies. Muscle biopsy samples were assessed by immunohistochemistry, immunoblotting, and real‐time quantitative polymerase chain reaction. Negative regulators of type I IFN (ISG15 and USP18) and positive regulators of type I IFN (DDX58 and IFIH1) were analyzed.

Results

ISG15 expression discriminated patients with juvenile IIM from those with nonimmune myopathies and, among patients with juvenile IIM, discriminated those with DM from those with OM. Among patients with juvenile DM, up‐regulation of the type I IFN positive regulators DDX58 and IFIH1 was similar regardless of MSA status. In contrast, the highest levels of the type I IFN negative regulator ISG15 were observed in patients who were positive for melanoma differentiation–associated gene 5 (MDA‐5). Finally, ISG15 levels were inversely correlated with the severity of muscle histologic abnormalities and positively correlated with motor performance as evaluated by the Childhood Myositis Assessment Scale and by manual muscle strength testing.

Conclusion

Muscle ISG15 expression is strongly associated with juvenile DM, with patients exhibiting a different ISG‐15 muscle signature according to their MSA class. Patients with juvenile DM who are positive for MDA‐5 have higher expression of ISG15 in both gene form and protein form compared to the other subgroups. Moreover, our data show that negative regulation of type I IFN correlates with milder muscle involvement.
Neural Correlates of Audiovisual Temporal Binding Window in Individuals With Schizotypal and Autistic Traits: Evidence From Resting‐State Functional Connectivity
Authors: Zhou Han‐yu , Wang Yong‐ming , Zhang Rui‐ting , Cheung Eric F. C. , Pantelis Christos , Chan Raymond C. K.
Published: December 2020

Temporal proximity is an important clue for multisensory integration. Previous evidence indicates that individuals with autism and schizophrenia are more likely to integrate multisensory inputs over a longer temporal binding window (TBW). However, whether such deficits in audiovisual temporal integration extend to subclinical populations with high schizotypal and autistic traits are unclear. Using audiovisual simultaneity judgment (SJ) tasks for nonspeech and speech stimuli, our results suggested that the width of the audiovisual TBW was not significantly correlated with self‐reported schizotypal and autistic traits in a group of young adults. Functional magnetic resonance imaging (fMRI) resting‐state activity was also acquired to explore the neural correlates underlying inter‐individual variability of TBW width. Across the entire sample, stronger resting‐state functional connectivity (rsFC) between the left superior temporal cortex and the left precuneus, and weaker rsFC between the left cerebellum and the right dorsal lateral prefrontal cortex were correlated with a narrower TBW for speech stimuli. Meanwhile, stronger rsFC between the left anterior superior temporal gyrus and the right inferior temporal gyrus was correlated with a wider audiovisual TBW for non‐speech stimuli. The TBW‐related rsFC was not affected by levels of subclinical traits. In conclusion, this study indicates that audiovisual temporal processing may not be affected by autistic and schizotypal traits and rsFC between brain regions responding to multisensory information and timing may account for the inter‐individual difference in TBW width.

Lay summary

Individuals with ASD and schizophrenia are more likely to perceive asynchronous auditory and visual events as occurring simultaneously even if they are well separated in time. We investigated whether similar difficulties in audiovisual temporal processing were present in subclinical populations with high autistic and schizotypal traits. We found that the ability to detect audiovisual asynchrony was not affected by different levels of autistic and schizotypal traits. We also found that connectivity of some brain regions engaging in multisensory and timing tasks might explain an individual's tendency to bind multisensory information within a wide or narrow time window. Autism Res 2021, 14: 668–680. © 2020 International Society for Autism Research and Wiley Periodicals LLC
Dose range finding approach for rodent preweaning juvenile animal studies
Authors: Posobiec Lorraine M. , Laffan Susan B.
Published: December 2020

Objectives

Strategies for conducting juvenile dose ranging studies before definitive toxicity juvenile animal studies (JAS) have evolved, but the aim of demonstrating study design robustness and efficient animal use remains the same. The objective of dose selection is to identify a strategy to achieve consistent systemic exposure for the duration of the JAS while maintaining exposure separation between dose groups. For preweaning rodents this can prove challenging, as these studies typically treat animals over a broad period of considerable organ development.

Materials and Methods

In our experience, over 45 rodent juvenile studies (dose range, definitive or investigative) were conducted over 20 years to support pediatric medicine development. In most cases (86%, 12/14), preweaning rodents required decreased doses of test articles than adult rodents; the majority (83%, 10/12) were due to increased systemic exposures in immature animals at the same doses. Thus, extrapolating tolerability and exposure data from adults is not ideal and should not take the place of well‐designed juvenile dose range studies.

Results/Discussion/Conclusion

We propose a phased dose‐range‐finding approach by first conducting a tolerability phase with a few animals at a starting age corresponding to the youngest clinical starting age, spanning a wide range of doses, then a dose range phase with larger group sizes and fewer doses; both phases incorporate toxicokinetics. Often, exposure was higher in preweaning animals and decreased as animals matured postweaning (postnatal day, PND 21 and older), supporting an age‐based dose adjustment strategy. Case studies demonstrate dose adjustment approaches incorporating dose increases or decreases or changes in dose frequency.
A comparison of methods for analysing multiple outcome measures in randomised controlled trials using a simulation study
Authors: Vickerstaff Victoria , Ambler Gareth , Omar Rumana Z.
Published: December 2020

Multiple primary outcomes are sometimes collected and analysed in randomised controlled trials (RCTs), and are used in favour of a single outcome. By collecting multiple primary outcomes, it is possible to fully evaluate the effect that an intervention has for a given disease process. A simple approach to analysing multiple outcomes is to consider each outcome separately, however, this approach does not account for any pairwise correlations between the outcomes. Any cases with missing values must be ignored, unless an additional imputation step is performed. Alternatively, multivariate methods that explicitly model the pairwise correlations between the outcomes may be more efficient when some of the outcomes have missing values. In this paper, we present an overview of relevant methods that can be used to analyse multiple outcome measures in RCTs, including methods based on multivariate multilevel (MM) models. We perform simulation studies to evaluate the bias in the estimates of the intervention effects and the power of detecting true intervention effects observed when using selected methods. Different simulation scenarios were constructed by varying the number of outcomes, the type of outcomes, the degree of correlations between the outcomes and the proportions and mechanisms of missing data. We compare multivariate methods to univariate methods with and without multiple imputation. When there are strong correlations between the outcome measures (ρ > .4), our simulation studies suggest that there are small power gains when using the MM model when compared to analysing the outcome measures separately. In contrast, when there are weak correlations (ρ < .4), the power is reduced when using univariate methods with multiple imputation when compared to analysing the outcome measures separately.
Reactivity of Flavonoids Containing a Catechol or Pyrogallol Moiety with Metal‐Free and Metal‐Associated Amyloid‐β
Authors: Park Seongmin , Yi Yelim , Lim Mi Hee
Published: December 2020

Aggregates of both metal‐free amyloid‐β (Aβ) and metal‐bound Aβ (metal–Aβ) are accumulated in the brain affected by Alzheimer's disease. To control metal‐free and metal‐bound Aβ species, chemical reagents capable of modulating their aggregation profiles have been developed. As an effort, the reactivity of natural products such as flavonoids with metal‐free Aβ and metal–Aβ has been investigated to identify their use as chemical reagents and structural features essential for such reactivity. This review illustrates the effects of flavonoids containing a catechol or pyrogallol group on metal‐free and metal‐mediated Aβ aggregation pathways. In addition, the studies regarding the structure–activity relationship of flavonoids against metal‐free Aβ or metal–Aβ are discussed.
Revitalizing the common peroneal function index for assessing functional recovery following nerve injury
Authors: Fontaine Calder , Yeager Eric A. , Sledziona Michael , Jones Amanda K. , Cheetham Jonathan
Published: December 2020

Background and Aims

Peripheral nerve injury is common with poor functional recovery and consequent high personal and societal costs. Sciatic nerve transection and assessment of recovery using sciatic functional index (SFI) are widely used. SFI is biologically limited as axonal misdirection of axons supplying flexors and extensors in the hindlimb, after nerve injury can lead to synkinetic innervation and function which does not correspond to the degree of axonal regeneration.

Methods

We reevaluated the use of traditional metrics such as print length (PL), toe spread (TS), and intermediate toe spread (ITS) as well as hock angle at mid‐swing as approaches for determining recovery. We used two alternative approaches in discrete cohorts of rats following common peroneal crush injury, transection with repair and critical gap, using transection with ligation as a negative control. We compared walking track analysis (print) with digital capture and kinematics.

Results

PL, TS, and ITS varied as expected after injury. The traditional functional index for common peroneal injury using inked prints failed to describe recovery and we derived new indices to describe recovery (all R2 > 0.88, p < .0001) although pre‐injury PFI was never attained by any of the models. Kinematic analysis identified hock angle at mid‐swing as a useful predictor of recovery (p < .0001).

Interpretation

Using complementary approaches.
The effect of motor interference therapy in traumatic memories: A pilot study
Authors: Morales‐Rivero Alonso , Reyes‐Santos Lorena , Bisanz Erik , Ruiz‐Chow Angel , Crail‐Melendez Daniel
Published: December 2020

Introduction

Traumatic memories of events such as a life‐threatening incident, serious injury, or sexual violence are a core symptom of stress‐related disorders; they might be susceptible to positive modification with interference tasks (reconsolidation‐based interventions). Our objective was to test the effect of performing a motor interference task (finger tapping in response to audio cues) on patients who suffer from traumatic memories.

Methods

We designed an uncontrolled pilot prospective clinical trial. Ten participants listened to an audio track that instructed them to tap their fingers in response to specific audio cues while trying to recall the traumatic event. Each patient underwent an assessment including the Spanish version of the PTSD Symptom Severity Scale‐Revised (EGS‐R), the visual analogue scale (EQ‐VAS) from EuroQol 5D (EQ‐5D), and a simple visual analogue scale (VAS) before the intervention, immediately after, and a week after the treatment.

Results

All measures exhibited a statistically significant improvement 1 week after the study. On the PTSD scale, 1 week later, 30% of the patients did not score high enough for such diagnosis. The VAS measured immediately following the intervention (4.4, SD = 2.22) also improved (p < .001), and 30% of the patients scored zero. One week after the intervention, the VAS improved more than 50%

Conclusion

The rapid 1‐week improvement on the PSTD scale and the VAS after a 30 min intervention support the idea of further research using a double‐blind, controlled design powered to demonstrate the efficacy of motor interference, an easy‐to‐apply therapeutic tool, in the treatment of traumatic memories.
Exostosin1 as a novel prognostic and predictive biomarker for squamous cell lung carcinoma: A study based on bioinformatics analysis
Authors: Wu Disheng , Huo Chao , Jiang Siyu , Huang Yanxia , Fang Xuehong , Liu Jun , Yang Min , Ren Jianwei , Xu Bilian , Liu Yi
Published: December 2020

The exostosin (EXT) protein family is involved in diverse human diseases. However, the expression and prognostic value of EXT genes in human lung squamous cell carcinoma (LUSC) is not well understood. In this study, we analyzed the association between expression of EXT1 and EXT2 genes and survival in patients with LUSC using bioinformatics resources such as Oncomine and The Cancer Genome Atlas (TCGA) databases, the Gene Expression Profiling Interactive Analysis (GEPIA) server and Kaplan–Meier plotter. Furthermore, regulatory microRNAs (miRNAs) were predicted for EXT1 and used to establish a potential miRNA‐messenger RNA (mRNA) regulation network for LUSC using the ENCORI platform. We observed that EXT1 and EXT2 expression levels were higher in LUSC than those in normal tissues. However, only EXT1 expression was significantly associated with poor overall survival (OS) in LUSC patients. Functional annotation enrichment analysis showed that genes co‐expressed with the EXT1 gene were enriched in biological processes such as cell adhesion and migration, and KEGG pathways such as extracellular matrix receptor interactions, complement and coagulation cascades, and cell death. Furthermore, three miRNAs, hsa‐mir‐190a‐5p, hsa‐mir‐195‐5p, and hsa‐mir‐490‐3p, were identified to be potentially involved in the regulation of EXT1. In summary, we identified EXT1 expression as a novel potential prognostic marker for human LUSC and the regulatory miRNAs that could possibly contribute to the prognosis of the disease.
KeyFrame extraction for human motion capture data via multiple binomial fitting
Authors: Xu Chenxu , Yu Wenjie , Li Yanran , Lu Xuequan , Wang Meili , Yang Xiaosong
Published: December 2020

In this paper, we make two contributions. The first is to propose a new keyframe extraction algorithm, which reduces the keyframe redundancy and reduces the motion sequence reconstruction error. Secondly, a new motion sequence reconstruction method is proposed, which further reduces the error of motion sequence reconstruction. Specifically, we treated the input motion sequence as curves, then the binomial fitting was extended to obtain the points where the slope changes dramatically in the vicinity. Then we took these points as inputs to obtain keyframes by density clustering. Finally, the motion curves were segmented by keyframes and the segmented curves were fitted by binomial formula again to obtain the binomial parameters for motion reconstruction. Experiments show that our methods outperform existing techniques, in terms of reconstruction error.
Self‐expanding transcatheter aortic valve infolding: Current evidence, diagnosis, and management
Authors: Ancona Marco Bruno , Beneduce Alessandro , Romano Vittorio , Buzzatti Nicola , Russo Filippo , Bellini Barbara , Ferri Luca Angelo , Agricola Eustachio , Landoni Giovanni , Scandroglio Anna Mara , Chieffo Alaide , Montorfano Matteo
Published: December 2020

Background

Prosthetic valve infolding is a rare but severe complication of transcatheter aortic valve implantation (TAVI) with self‐expanding valves. However, currently available clinical data are limited and fragmented.

Objectives

This report aims to provide a comprehensive overview of this complication focusing on predisposing factors, clinical presentation, diagnostic findings, treatment and clinical outcomes.

Methods

A systematic review of the literature was performed to identify cases of infolding occurring during TAVI with self‐expanding valves published until August 2020. These data were pooled with all the retrospectively identified infolding cases occurred at San Raffaele Scientific Institute between December 2014 and August 2020.

Results

A total of 34 cases were included. Among patients with available data, 38% received a first‐generation CoreValve, and 62% a second‐generation Evolut R (82%) or Evolut PRO (18%). Infolding occurred mostly with ≥29‐mm valves (94%). Predisposing factors included resheathing of a second‐generation valve (82%), heavy calcification of the native valve (65%), lack of predilatation (16%), Sievers type‐1 bicuspid aortic valve (11%), and improper valve loading (5%). Infolding resulted in severe PVL causing hemodynamic instability (29%) or cardiac arrest (12%). Postdilatation was the treatment strategy in 68%, while prosthesis replacement with a new device in 23% of cases. Device success rate was 82%. Death and stroke occurred in 3% and 12% of cases.

Conclusions

Prosthetic valve infolding is typically observed after resheathing of a large‐size self‐expanding TAVI. When infolding is timely diagnosed, prosthesis removal and replacement should be pursued. Further studies are required to precisely define predisposing factors to prevent this complication.
Insight into the Metal‐Support Interactions between Ruthenium and Nanodiamond‐derived Carbon material for CO Oxidation
Authors: Zhang Liyun , Wu Kuang‐Hsu , Ding Yuxiao , Shi Wen , Liu Siyang , Niu Yiming , Zhang Bingsen
Published: December 2020

For supported metal catalysts, metal‐support interactions (MSI) are vital for their catalytic performance, which can be regulated by controlling surface structures of supports. In this work, two kinds of nanodiamond (ND)‐derived carbon materials, i. e. ND@graphene (ND@G) and onion‐like carbon (OLC), were applied to support Ru catalyst. The characterization results show that compared with OLC supported Ru catalyst (Ru/OLC), ND@G supported Ru catalyst (Ru/ND@G) exhibits a higher Ru dispersity, large amount of nanoclusters and Ru single atoms with positive charges dispersing on the surface of ND@G, indicating a stronger MSI in Ru/ND@G. Ru/ND@G favors twin CO adsorbates, while Ru/OLC favors linear adsorbates. For CO oxidation reaction, it was found that Ru/OLC with more metallic Ru NPs exhibited higher catalytic activity compared to Ru/ND@G. Moreover, Ru/OLC showed better reusability and stability compared to Ru/ND@G during CO oxidation reaction. This work highlights the importance of having an adequate rather than an excessively strong MSI for some catalytic systems.
Structural Exploration of Multilayered Ionic Liquid/Ag Electrode Interfaces by Atomic Force Microscopy and Surface‐Enhanced Raman Spectroscopy
Authors: Zhang Meng , Duan Sai , Luo Siheng , Zhong Yunxin , Yan Jiawei , Liu Guokun , Mao Bingwei , Tian Zhongqun
Published: December 2020

Experimentally and theoretically exploring the detailed structure of ionic liquid/electrode interfaces is challenging. Progress has been made in understanding inner two‐dimensional ionic liquid/electrode interfaces. However, few studies have investigated the multilayer structure of the ionic liquid/electrode interface, which requires high spatial and chemical resolution. Here, using the interface structure of 1‐ethyl‐3‐methylimidazolium bis‐trifluoromethylsulfonyl imide (EMITFSI)/Ag (111) as a model system, its multilayer structure was revealed by in situ atomic force microscopy (AFM) and molecular dynamics simulations. The potential‐dependent interfacial orientations of the first and second EMITFSI layers were determined by electrochemical shell‐isolated nanoparticles‐enhanced Raman spectroscopy (SHINERS) on Ag(111) and surface‐enhanced Raman spectroscopy (SERS) on Ag nanoparticles. This work shows that a clear multilayer structure of ionic liquid/electrode interfaces can be explored by combining multiple techniques.
PD‐1 blockade using pembrolizumab in adolescent and young adult patients with advanced bone and soft tissue sarcoma
Authors: Scheinberg Tahlia , Lomax Anna , Tattersall Martin , Thomas David , McCowage Geoff , Sullivan Michael , Karim Rooshdiya , Luk Peter P. , Mahar Annabelle , Bonar Fiona , Bhadri Vivek A.
Published: December 2020

Background

Sarcomas represent 10%–15% of cancers in adolescent and young adult (AYA) patients, and survival for those with metastatic disease or relapse is poor. Immunotherapy with checkpoint inhibition has improved outcomes in multiple tumor types, but data in advanced sarcomas, particularly within the AYA population, are limited.

Aim

We aim to evaluate response and toxicity for AYA patients with sarcoma treated with pembrolizumab.

Methods and results

We retrospectively reviewed AYA patients with advanced bone and soft tissue sarcoma who received self‐funded pembrolizumab between May 2015 and January 2019. Eighteen patients were identified. One patient with Ewing sarcoma had a sustained complete response to therapy. Two patients with alveolar soft part sarcoma received a clinical benefit from pembrolizumab: one had a radiological partial response with an excellent clinical response and one patient achieved stable disease. Four patients died of disease prior to first scheduled assessment and thus were not evaluable. The remaining eleven patients had progressive disease.

Conclusion

The role of immunotherapy in AYA sarcoma warrants further investigation. Biomarkers of response need to be further evaluated in order to guide patient selection.
Stimulants increasingly involved in opioid OD deaths in teens and young adults
Authors: Knopf Alison
Published: December 2020

The first study characterizing polysubstance involvement in opioid overdose deaths among youth has found that in 2018, for the first time, these OD deaths were more prevalent than those involving opioids alone. And, surprisingly, it was not other central nervous system depressants (e.g., alcohol, benzodiazepines) that were most commonly involved. It was stimulants.
Prognostic and therapeutic considerations of antibodies against c‐ter apolipoprotein A‐1 in the general population
Authors: Vuilleumier Nicolas , Antiochos Panagiotis , Marques‐Vidal Pedro , Pagano Sabrina , Virzi Julien , Satta Nathalie , Hartley Oliver , Gaertner Hubert , Brandt Karim J , Burger Fabienne , Montecucco Fabrizio , Waeber Gerard , Mach François , Vollenweider Peter
Published: December 2020

Objectives

Autoantibodies against apolipoprotein A1 (anti‐apoA1 IgGs) and its C‐terminal region (cter apoA1) have emerged as an independent biomarker for cardiovascular disease. Cter apoA1 mimetic peptides were shown to reverse the deleterious anti‐apoA1 IgG effects in vitro. We evaluated the association of anti‐cter apoA1 IgGs with overall mortality in the general population and tested the ability of a cter apoA1 mimetic peptide to reverse the anti‐apoA1 IgG‐induced inflammatory response and mortality in vitro and in vivo, respectively.

Methods

Anti‐cter apoA1 IgGs were measured in serum samples of 6386 participants of the CoLaus study of which 5220 were followed for a median duration of 5.6 years. The primary outcome was overall mortality. The peptide inhibitory concentration 50% (IC50) was determined in vitro on HEK‐Blue‐4 and RAW cells. ApoE−/− mice were exposed to 16 weeks of anti‐apoA1IgG passive immunisation with and without peptide co‐incubation.

Results

Anti‐cter apoA1 IgGs were associated with higher interleukin 6 levels and independently predicted overall mortality; an increase of one standard deviation of anti‐cter apoA1 IgG level was associated with an 18% increase in mortality risk (hazard ratio: 1.18, 95% confidence interval: 1.04–1.33; P = 0.009). The cterApoA1 analogue reversed the antibody‐mediated inflammatory response with an IC50 of 1 µm in vitro but did not rescue the significant anti‐apoA1 IgG‐induced mortality rate in vivo (69% vs. 23%, LogRank P = 0.02).

Conclusion

Anti‐cter apoA1 IgG independently predicts overall mortality in the general population. Despite being effective in vitro, our cter apoA1 analogue did not reverse the anti‐apoA1 IgG‐induced mortality in mice. Our data suggest that these autoantibodies are not readily treatable through cognate peptide immunomodulation.
Ultrathin Metal Silicate Hydroxide Nanosheets with Moderate Metal–Oxygen Covalency Enables Efficient Oxygen Evolution
Authors: Zhu Jiexin , Li Shikun , Zhuang Zechao , Gao Shan , Hong Xufeng , Pan Xuelei , Yu Ruohan , Zhou Liang , Moskaleva Lyudmila V. , Mai Liqiang
Published: December 2020

Exploring efficient, cost‐effective, and durable electrocatalysts for electrochemical oxygen evolution reaction (OER) is pivotal for the large‐scale application of water electrolysis. Recent advance has demonstrated that the activity of electrocatalysts exhibits a strong dependence on the surface electronic structure. Herein, a series of ultrathin metal silicate hydroxide nanosheets (UMSHNs) M3Si2O5(OH)4 (M = Fe, Co, and Ni) synthesized without surfactant are introduced as highly active OER electrocatalysts. Cobalt silicate hydroxide nanosheets show an optimal OER activity with overpotentials of 287 and 358 mV at 1 and 10 mA cm−2, respectively. Combining experimental and theoretical studies, it is found that the OER activity of UMSHNs is dominated by the metal–oxygen covalency (MOC). High OER activity can be achieved by having a moderate MOC as reflected by a σ*‐orbital (eg) filling near unity and moderate [3d]/[2p] ratio. Moreover, the UMSHNs exhibit favorable chemical stability under oxidation potential. This contribution provides a scientific guidance for further development of active metal silicate hydroxide catalysts.
The Electronic Properties of Ni(PNN) Pincer Complexes Modulate Activity in Catalytic Hydrodehalogenation Reactions
Authors: Wang Denan , Gardinier James R.
Published: December 2020

Three chloronickel(II) complexes of PNN‐ pincer ligands with pyrazolyl and diphenylphosphino donors appended to different arms of diarylamido anchors were prepared and fully characterized. The three derivatives (1‐OMe, 1‐Me, 1‐CF3) differ only by the identity of the para‐aryl substituent on the pyrazolyl arm with 1‐OMe being 310 mV easier to oxidize than 1‐CF3. All three complexes are competent catalysts for hydrodehalogenation reactions of 1‐bromooctane and a variety of aryl halides in dimethylacetamide using NaBH4 as both base and hydride source. Comparative studies using diverse substrates showed that catalytic activity correlates with electron donor properties; 1‐OMe was superior to the other two. Deuterium labeling studies verified NaBD4 as the deuteride source and excluded solvent‐assisted radical pathways.
Structural and Energetic Features of Group 13 Element Trispentafluorophenyl Complexes with Diethyl Ether
Authors: Kazakov Igor V. , Lisovenko Anna S. , Shcherbina Nadezhda A. , Kornyakov Ilya V. , Gugin Nikita Y. , Kondrat'ev Yurii V. , Chernysheva Anna M. , Zavgorodnii Artem S. , Timoshkin Alexey Y.
Published: December 2020

The complexes of group 13 element trispentafluorophenyl derivatives E(C6F5)3 (E = B, Al, Ga, In) with diethyl ether of 1:1 composition have been synthesized and structurally characterized. All compounds are isostructural. Thermal stability studies reveal that at elevated temperatures all complexes decompose with pentafluorobenzene evolution. The geometries and thermodynamic characteristics for the dissociation reactions of the compounds have been computed using three DFT methods. The 1H NMR α‐proton chemical shifts for the coordinated ether in deuteriobenzene and in CD2Cl2 solutions correlate with gas phase dissociation enthalpies of the complexes. Potentially high Lewis acidity of B(C6F5)3 is hindered by the large pyramidalization energy of the acceptor moiety.
Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains
Authors: Scheibe Benjamin , Haiges Ralf , Ivlev Sergei I. , Karttunen Antti J. , Müller Ulrich , Christe Karl O. , Kraus Florian
Published: December 2020

Difluorochloronium(III) compounds were synthesized from the reaction of metal powders (Ru, Os, Ir, Au), metal fluorides (NbF5, SbF3, BiF5) or a metal chloride (TaCl5) with excess liquid chlorine trifluoride. The compounds ClF2[AuF4], ClF2[MF6] (M = Nb, Ta, Ru, Os, Ir, Sb, Bi) and ClF2[Ta2F11] were obtained in crystalline form and their crystal structures were determined by single‐crystal X‐ray diffraction. The ClF2+ cations in the investigated compounds are bent, containing two strong, short, mainly covalent Cl–F bonds and two sterically active, free valence electron pairs in a pseudo‐tetrahedral arrangement. The coordination around the Cl atom is extended by two highly ionic, long fluorine bridges to neighboring fluoridometallate anions, resulting in a total coordination number of six. The crystal structures vary among the ClF2+ compounds and range from molecular building blocks, such as dimeric (ClF2[AuF4])2 and (ClF2[Ta2F11])2, to chains, some of which being helical, as in ClF2[MF6], (M = Nb, Ta, Ru, Os, Ir, Sb, Bi). Quantum‐chemical solid‐state and gas‐phase calculations were carried out to elucidate the bonding within the ClF2+ cations and their interactions with the bridging F atoms.
Metal‐Free Synthesis of Unsymmetrical Aryl Selenides and Tellurides via Visible Light‐Driven Activation of Arylazo Sulfones
Authors: Liu Junjie , Tian Miaomiao , Li Yuxuan , Shan Xiwen , Li Ankun , Lu Kui , Fagnoni Maurizio , Protti Stefano , Zhao Xia
Published: December 2020

A protocol for the visible light driven preparation of unsymmetrical (hetero)aryl selenides and tellurides is described herein. The method exploits the peculiar photoreactivity of arylazo sulfones that act as thermally stable, precursors of aryl radicals under both photocatalyst‐ and additive‐free conditions. The method developed shows an impressive versatility (more than fifty compounds isolated).
Multivalent 1,2,3‐Triazole‐Linked Carbohydrate Mimetics by Huisgen–Meldal‐Sharpless Cycloadditions of an Azidopyran
Authors: Salta Joana , Arp Fabian F. , Kühne Christian , Reissig Hans‐Ulrich
Published: December 2020

Starting from an enantiopure 3‐azido‐substituted pyran derivative and various oligo‐alkynes a series of multivalent 1,2,3‐triazole‐linked carbohydrate mimetics was synthesized. The copper‐catalyzed Huisgen–Meldal‐Sharpless cycloaddition (CuAAC) served as key coupling reaction. Cu/C in the presence of triethylamine proved to be a good catalytic system in most cases. Tri‐, tetra‐, hexa‐, and octavalent compounds with typical rigid or flexible core units were prepared. The most complex compound contains a C60‐fullerene center leading to a dodecavalent carbohydrate mimetic. Only a few of the multivalent target compounds could be converted into pure O‐sulfated derivatives that are required for their evaluation as L‐ and P‐selectin ligands. Nevertheless, preliminary experiments suggest that the dodecavalent C60‐derived compound may be a promising ligand of these biologically important proteins with IC50 values in the low nanomolar range.
Metal‐Free Selective and Diverse Synthesis of Three Distinct Sets of Isoindolinones from 2‐Alkynylbenzoic Acids and Amines
Authors: Jia Xiuwen , Li Pinyi , Zhang Xiaoning , Liu Siyu , Shi Xingzi , Ma Wenbo , Dong Hongbo , Lu Yangbin , Ni Hangcheng , Zhao Fei
Published: December 2020

The metal‐free selective and diverse synthesis of three distinct sets of isoindolinones from 2‐alkynylbenzoic acids and amines has been achieved in a reaction‐condition‐controlled manner. This method exhibits valuable advantageous features such as available starting materials, broad substrate scope, excellent selectivity, good to high yields, good functional group tolerance, simple operation, high bond‐forming efficiency, and step economy, thus providing a convenient and efficient access to a variety of heterocyclic compounds incorporating the bioactive isoindolinone motif.
A Novel Approach to N‐Tf 2‐Aryl‐2,3‐Dihydroquinolin‐ 4(1H)‐ones via a Ligand‐Free Pd(II)‐Catalyzed Oxidative Aza‐Michael Cyclization
Authors: Kim Young Min , Yoo Hyung‐Seok , Son Seung Hwan , Kim Ga Yeong , Jang Hyu Jeong , Kim Dong Hwan , Kim Soo Dong , Park Boyoung Y. , Kim Nam‐Jung
Published: December 2020

2‐Aryl‐2,3‐dihydroquinolin‐4(1H)‐ones have recently been identified as important structures with potent biological activities such as antitumor and antidiabetic effect. Herein, a total of 25 novel N‐Tf 2‐aryl‐2,3‐dihydroquinolin‐4(1H)‐ones were expediently synthesized via the oxidative aza‐Michael cyclization of N‐Tf‐2′‐aminodihydrochalcones by ligand‐free palladium(II) catalysis. This study presents a new synthetic approach to yield N‐Tf 2‐aryl‐2,3‐dihydroquinolin‐4(1H)‐ones, which can be easily transformed into pharmacologically interesting aza‐flavanones and other N‐heterocycles, such as quinolines and tetrahydroquinolines, in yields up to 84 %. This methodology has various advantages, which includes short reaction times under mild conditions and suitable functional group tolerance. Furthermore, a plausible mechanism was proposed and demonstrated by kinetic analysis.
Distinct element modeling of the dynamic response of a rocking podium tested on a shake table
Authors: Malomo Daniele , Mehrotra Anjali , DeJong Matthew J.
Published: December 2020

A blind prediction contest was organized to evaluate the ability of different modeling approaches to simulate the seismic rocking response of a full‐scale four‐column podium structure. The structure was tested on a shake table, and was subjected to two bidirectional ground motion ensembles comprising 100 synthetic records each. This short communication presents the main assumptions and results from the model, developed using the distinct element method, which provided the second‐best prediction of the experimental results. A comparison of the model predictions and the experimental results demonstrates that the numerical model was generally able to reproduce the large displacements induced by the more intense ground motion ensemble, while tending to overestimate the displacements of the less intense earthquake ensemble. This overestimation of the response was reduced through the inclusion of damping in the system. However, the addition of damping greatly increased the solve time, which is problematic for a competition, and in the case of the more intense ground motion ensemble also resulted in an underprediction of the maximum response of the structure.
An experimental investigation for a hybrid phase change material‐liquid cooling strategy to achieve high‐temperature uniformity of Li‐ion battery module under fast charging
Authors: Chen Siqi , Garg Akhil , Gao Liang , Wei Xuezhe
Published: December 2020

Fast charging is significant for the convenience of long‐term driving. In this study, a hybrid‐phase change material (PCM)‐liquid cooling system is designed for a battery module with eight prismatic cells under high charging current rates. Temperature rise, temperature distribution, and energy consumption of the cooling system are measured in experiments under 3C, 2.5C, and 2C fast charging. The results indicate that the highest coolant flow rate and the largest PCM thickness cannot achieve the optimal thermal performance. Therefore, appropriate coolant flow rate and PCM thickness selection ensure the cooling performance and reduce energy mass and volume consumption. Experimental results demonstrate that the maximum temperature of the module can be decreased from 43°C to 35.6°C, 34.5°C, and 34.8°C by pure PCM, pure liquid cooling, and the hybrid PCM‐liquid cooling system under 3C fast charging; and temperature standard deviation (TSD) can be controlled within 0.9°C, 1.5°C, and 0.96°C, respectively. When the PCM thickness and coolant flow rate are set as 0.65 mm and 54 mL/min, respectively, the hybrid cooling system achieves the optimal thermal performance (maximum temperature: 34.8°C, TSD: 1°C) under 3C fast charging, and the energy consumption (459 J) can be controlled within the acceptable range.
Forecasting China's Crude Oil Futures Volatility: The Role of the Jump, Jumps Intensity, and Leverage Effect
Authors: Wang Jiqian , Ma Feng , Wahab M.I.M. , Huang Dengshi
Published: December 2020

This study explores the forecasting ability of jump, jump intensity, and leverage effect for an emerging futures market, China's crude oil futures market, using different kinds of HAR‐type models. From an in‐sample perspective, we find that the HAR components, monthly leverage effect, jump size, and jump intensity have positive effects on future oil volatility. Moreover, out‐of‐sample results show that a forecasting model with jump and jump intensity cannot only achieve a superior forecasting performance under low volatility level but also increase the economic value. Subsequently, we examine the effect of decompositions of jump information, the results show signed jump components can improve the accuracy. Finally, we extend our empirical analysis considering different forecast horizons, COVID‐19 pandemic, and different trading hours. Our empirical results are robust and consistent.
Advances in Solar‐Driven Hygroscopic Water Harvesting
Authors: Zhuang Shendong , Qi Heshan , Wang Xueyang , Li Xiuqiang , Liu Kai , Liu Jun , Zhang Han
Published: December 2020

Water scarcity is one of the greatest global challenges at this time. Significant efforts have been made to harvest water from the air, due to widely available water sources present in the atmosphere. Particularly, solar‐driven hygroscopic water harvesting based on the adsorption–desorption process has gained tremendous attention because of the abundance of solar energy in combination with substantial improvements in conversion efficiency enabled by advanced sorbents, improved photothermal materials, interfacial heating system designs, and thermal management in recent years. Here, recent developments in atmospheric water harvesting are discussed, with a focus on solar‐driven hygroscopic water harvesting. The diverse structural designs and engineering strategies that are being used to improve the rate of the water production, including the design principles for sorbents with high adsorption capacity, high‐efficiency light‐to‐heat conversion, optimization of thermal management, vapor condensation, and water collection, are also explored. The current challenges and future research opportunities are also discussed, providing a roadmap for the future development of solar‐driven hygroscopic water harvesting technology.
Dynamic transcriptome landscape in the song nucleus HVC between juvenile and adult zebra finches
Authors: Shi Zhimin , Zhang Zeyu , Schaffer Lana , Huang Zhi , Fu Lijuan , Head Steven , Gaasterland Terry , Wang Xiu‐Jie , Li XiaoChing
Published: December 2020

Male juvenile zebra finches learn to sing by imitating songs of adult males early in life. The development of the song control circuit and song learning and maturation are highly intertwined processes, involving gene expression, neurogenesis, circuit formation, synaptic modification, and sensory‐motor learning. To better understand the genetic and genomic mechanisms underlying these events, we used RNA‐Seq to examine genome‐wide transcriptomes in the song control nucleus HVC of male juvenile (45 d) and adult (100 d) zebra finches. We report that gene groups related to axon guidance, RNA processing, lipid metabolism, and mitochondrial functions show enriched expression in juvenile HVC compared to the rest of the brain. As juveniles mature into adulthood, massive gene expression changes occur. Expression of genes related to amino acid metabolism, cell cycle, and mitochondrial function is reduced, accompanied by increased and enriched expression of genes with synaptic functions, including genes related to G‐protein signaling, neurotransmitter receptors, transport of small molecules, and potassium channels. Unexpectedly, a group of genes with immune system functions is also developmentally regulated, suggesting potential roles in the development and functions of HVC. These data will serve as a rich resource for investigations into the development and function of a neural circuit that controls vocal behavior.