bluuebunny/crossref_metadata_2025 huggingface dataset:
Yttrium‐Doped Barium Zirconate‐Cerate Solid Solution as Proton Conducting Electrolyte: Why Higher Cerium Concentration Leads to Better Performance for Fuel Cells and Electrolysis Cells
Authors: Han Donglin , Liu Xin , Bjørheim Tor Svendsen , Uda Tetsuya
Published: January 2021

Proton conducting Y‐doped BaZrO3, BaCeO3 and their solid solutions are receiving increasing attention due to their promising application as electrolytes in ceramic fuel cells and electrolysis cells. However, the literature indicates a clear tendency that the performance of the cells increases with increasing Ce content in the electrolyte. In this work, to elucidate this phenomenon, a systematic work is performed on investigating the phase, hydration, and transport behaviors of BaZr0.8−xCexY0.2O3−δ (BZCY20). The results reveal that in the temperature range between 500 and 700 °C, with increasing Ce content, the dehydration temperature elevates and the proton concentration increases, showing that the Ce component favors the stabilization of protons. Furthermore, the transport number of hole conduction decreases, whereas the transport number of ionic conduction increases with the increasing Ce content. By further separating the contribution of oxide ions and protons, it is found that the oxide ion conductivity increases with the increasing Ce content at higher temperatures of 600 and 700 °C. Such decreased hole conductivity and increased oxide ion conductivity result in the enhancement of the ionic conduction of BZCY20 with increasing Ce content, and therefore improve the performance of fuel cells and electrolysis cells.
Extrinsic‐Structured Bimetallic‐Phase Ternary Metal Phosphorus Trisulfides Coupled with N‐Doped Graphitized Carbon for Superior Electrochemical Lithium Storage
Authors: Gui Qiaoqiao , Feng Yutong , Chen Bingjie , Gu Feng , Chen Lu , Meng Shuo , Xu Mengzhu , Xia Mengting , Zhang Chi , Yang Jinhu
Published: January 2021

The exploration of advanced electrode materials through rational structure/phase design is the key to develop high‐performance rechargeable batteries. Herein, ternary metal phosphorus trisulfides (NiCoPS3) with a bimetallic phase and an extrinsic structure of nanodots combined with nitrogen‐doped graphitized carbon (NC) are developed for lithium‐ion batteries. The designed NiCoPS3/NC holding a nanocube‐like morphology shows a set of structural/compositional advantages as lithium‐ion battery anodes including high electrical conductivity, low ion diffusion barrier, improved theoretical lithium storage capacity, and relieved lithiation stress, which are confirmed by characterizations and density functional theory calculations. As a consequence, the NiCoPS3/NC electrode displays superior comprehensive lithium storage performance, e.g., high reversible capacity (991 mAh g−1 at 0.1 A g−1), excellent cycling stability (up to 1200 cycles at 2 A g−1 and 2000 cycles at 5 A g−1 with respective capacity retention of over or nearly 100%), and good rate capability (58.4% capacity retention after a current change from 0.1 to 5 A g−1), representing the best comprehensive battery performance in MPS3‐based anodes to date.
Boosting Energy Storage via Confining Soluble Redox Species onto Solid–Liquid Interface
Authors: Sun Shuo , Liu Bo , Zhang Hongshen , Guo Qiubo , Xia Qiuying , Zhai Teng , Xia Hui
Published: January 2021

An upswell in the demand for both high energy density and large power density has triggered extensive research in developing next‐generation energy storage systems (ESSs), including redox‐enhanced electrochemical capacitors, metal–sulfur (LiS and NaS) batteries, and metal–iodine (LiI2, NaI2, etc.) batteries, which involve a liquid reaction pathway that decouples the reaction kinetics from the sluggish ion diffusion in the solid phase. Development is plagued at present by the shuttle effects of soluble redox species (SRSs) resulting in poor cycling stability and rapid self‐discharge. Based on the shuttle mechanisms of SRSs, it is crucial to build an atomic or molecular relationship between the electrode surface and SRSs, that is, solid–liquid interface. Here, a timely review of current advances towards the confinement of SRSs in ESSs through solid–liquid interfacial manipulation at the atomic/molecular level is presented. Particularly, the immobilization mechanisms of SRSs around electrode materials within a series of successful examples are highlighted. The corresponding promising research avenues and challenges via interfacial manipulations are also outlined. With this work as a background, new insights into promising strategies that effectively confine the SRSs around electrodes are discussed, with the aim to facilitate vertical leaps in the performance of next‐generation ESSs.
Optimizing catalyst supports at single catalyst pellet and packed bed reactor levels: A comparison study
Authors: Liu Xinlei , Qin Bo , Zhang Qunfeng , Ye Guanghua , Zhou Xinggui , Yuan Weikang
Published: January 2021

Using a catalyst support with optimal pore network and pellet structures is critical to the success of an industrial heterogeneous catalyst. This work optimizes the catalyst support of a dry reforming of methane catalyst at packed bed reactor level, that is, effects of concentration and temperature gradients in the reactor are accounted for. Meanwhile, the optimization at reactor level is also compared with that at single catalyst pellet level where fixed concentrations and temperature are imposed on the pellet surface. Results show that the optimal structures obtained at pellet level are similar to these acquired at reactor level, but the improvements in catalyst performance calculated at pellet level are overestimated. Therefore, when designing an industrial catalyst pellet, the preferred structures can be obtained from the optimization at pellet level, but the corresponding improvements in catalyst performance should be evaluated at reactor level to reflect the reality in industry.
Machine learning modeling and predictive control of nonlinear processes using noisy data
Authors: Wu Zhe , Rincon David , Luo Junwei , Christofides Panagiotis D.
Published: January 2021

This work focuses on machine learning modeling and predictive control of nonlinear processes using noisy data. We use long short‐term memory (LSTM) networks with training data from sensor measurements corrupted by two types of noise: Gaussian and non‐Gaussian noise, to train the process model that will be used in a model predictive controller (MPC). We first discuss the LSTM training with noisy data following a Gaussian distribution, and demonstrate that the standard LSTM network is capable of capturing the underlying process dynamic behavior by reducing the impact of noise. Subsequently, given that the standard LSTM performs poorly on a noisy data set from industrial operation (i.e., non‐Gaussian noisy data), we propose an LSTM network using Monte Carlo dropout method to reduce the overfitting to noisy data. Furthermore, an LSTM network using co‐teaching training method is proposed to further improve its approximation performance when noise‐free data from a process model capturing the nominal process state evolution is available. A chemical process example is used throughout the manuscript to illustrate the application of the proposed modeling approaches and demonstrate their open‐ and closed‐loop performance under a Lyapunov‐based model predictive controller with state measurements corrupted by industrial noise.
Integrating pore interconnectivity and adaptability in a single crystal hierarchical zeolite for liquid alkylation
Authors: Liu Baoyu , Huang Jiajin , Liao Zhantu , Zhu Chongzhi , Chen Qiaoli , Sheng Guan , Zhu Yihan , Huang Yi , Dong Jinxiang
Published: January 2021

Zeolite belongs to one of the most important families of solid acid catalysts in chemical industries. It is, however, severely constrained by the diffusion limitation for bulky molecules, a lack of multifunctionality for sequential reactions and pore adaptability toward specific adsorbates due to its small micropore size and simple aluminosilicate framework. Introducing mesopores into a zeolite toward realizing hierarchical zeolites is a prevailing strategy but one that usually suffers from compromised crystallinity as well as insufficient interconnectivity and openness of the mesopores. Herein, a novel acid‐redox co‐functionalized single‐crystalline zeolite with highly open and interconnected mesopores is designed and fabricated. As a proof‐of‐concept study, we integrate solid acid and Fe‐oxy redox sites into a hierarchical MEL zeolite with well‐characterized microporosity and mesoporosity. This zeolite exhibits superior activity and stability toward alkylation between mesitylene with benzyl alcohol, arising from greatly facilitated intra‐crystal molecular diffusion, mitigated metal leaching and optimized adsorbate‐pore wall interactions.
Steady‐state and transient hydrothermal analyses of single‐phase natural circulation loop using water‐based tri‐hybrid nanofluids
Authors: Sahu Mayaram , Sarkar Jahar , Chandra Laltu
Published: January 2021

Transient and steady‐state characteristics of the natural circulation loop are studied using various water‐based tri‐hybrid (different nature and shaped nanoparticles) nanofluids. Effects of input power, loop inclination and loop aspect ratio on the mass flow rate, effectiveness, and entropy generation rate are studied. Results disclose that tri‐hybrid nanofluids reduce the oscillation and attain steady state faster than water. Effectiveness increases and entropy generation rate decreases by using tri‐hybrid nanofluids. Nanoparticle shape has found a significant impact. Al2O3 + Cu + CNT/water shows the best performance. The mass flow rate increases with input power, loop aspect ratio, whereas, reduces with loop inclination. Effectiveness decreases and then increases with input power, whereas increases with loop inclination and decreases with loop aspect ratio. Entropy generation upsurges with input power and loop inclination, whereas decreases with loop aspect ratio. Loop aspect ratio of 1.5 to 3 is found suitable for better performance.
Kinetics of aging process on reduced Ag exchanged mordenite in dry air and humid air
Authors: Choi Seungrag , Nan Yue , Tavlarides Lawrence L.
Published: January 2021

Aging effects of off‐gas streams including dry air and humid air on reduced silver exchanged mordenite (Ag0Z) were studied. Aged Ag0Z was prepared by exposing Ag0Z to dry air and humid air at different aging temperatures, time, and water vapor concentrations. Iodine loading capacity on the aged Ag0Z was obtained through a continuous‐flow adsorption system. Significant iodine loading capacity losses were observed after the Ag0Z was exposed to dry air and humid air. Physical and chemical analyses were conducted to observe the physical and chemical changes of Ag0Z after being aged. From iodine adsorption data and sample analyses, it was found that iodine loading capacity on the aged Ag0Z in dry air and humid air decreases with increasing aging temperatures, time, and water vapor concentrations. The pseudo reaction model describes experimental data well and the oxidation of Ag0 is the rate determining step in the aging process.
A phase I/II study of the combination of panobinostat and carfilzomib in patients with relapsed or relapsed/refractory multiple myeloma: Final analysis of second dose‐expansion cohort
Authors: Berdeja Jesus G. , Gregory Tara K. , Faber Edward A. , Hart Lowell L. , Mace Joseph R. , Arrowsmith Edward R. , Flinn Ian W. , Matous Jeffrey V.
Published: January 2021

The maximum tolerated dose of the panobinostat and carfilzomib combination in patients with relapsed/refractory multiple myeloma (RRMM) was not reached in our previous dose‐escalation study. We report additional dose levels in the phase I/II, single‐arm, multicenter, standard 3 + 3 dose‐escalation expansion‐cohort study (NCT01496118). Patients with RRMM were treated with panobinostat 30 mg, carfilzomib 20/56 mg/m2 (N = 3), or panobinostat 20 mg, carfilzomib 20/56 mg/m2 (N = 33). Treatment cycles lasted 28 days; panobinostat: days 1, 3, 5, 15, 17, 19; carfilzomib: days 1, 2, 8, 9, 15, 16. For dose level 6 (DL 6), median age was 63 years (range, 49–91 years), 60.6% were male, 42.4% were high risk. Patients received a median of two prior therapies (range 1–7); proteasome inhibitors (PI; 100%), immunomodulatory imide drugs (IMiD; 78.8%), and stem cell transplant (36.4%); 48.5%, 51.1%, and 24.2% were refractory to prior PI or prior IMiD treatment or both, respectively. Patients completed a median of seven (range 1–40) treatment cycles. Overall response rate (primary endpoint) of evaluable patients in the expansion cohort (N = 32): 84.4%; clinical benefit rate: 90.6%. With a median follow‐up of 26.1 months (range, 0–72.5 months), median (95% CI) progression‐free survival, time‐to‐progression and overall survival of patients was 10.3 (6.1, 13.9), 11.7 (5.6, 14.5), and 44.6 (20.8, N/A) months, respectively. Common adverse events (AEs) included thrombocytopenia (78.8%), nausea (63.6%), fatigue (63.6%), diarrhea (51.5%), and vomiting (51.5%). Seven patients had serious treatment‐related AEs. There was one treatment‐related death. In conclusion, panobinostat plus carfilzomib is an effective steroid‐sparing regimen for RRMM.
Comparison of the current renal staging, progression and response criteria to predict renal survival in AL amyloidosis using a Mayo cohort
Authors: Drosou Maria Eleni , Vaughan Lisa E. , Muchtar Eli , Buadi Francis K. , Dingli David , Dispenzieri Angela , Fonder Amie L. , Gertz Morie A. , Go Ronald S. , Gonsalves Wilson I. , Hayman Suzanne R. , Hobbs Miriam A. , Hwa Yi L. , Kapoor Prashant , Kourelis Taxiarchis , Kumar Shaji , Kyle Robert A. , Lacy Martha Q. , Lin Yi , Lopez Camden L. , Lust John A. , Rajkumar S. Vincent , Russell Stephen J. , Sidana Surbhi , Siddiqui Mustaqeem A. , Sidiqi M. Hasib , Warsame Rahma , Leung Nelson
Published: January 2021

Three sets of criteria (International Society of Amyloidosis [ISA], Palladini and Kastritis) were independently developed for staging, progression and response criteria to predict renal survival in patients with AL amyloidosis. We evaluated these criteria using a cohort of 495 newly diagnosed AL amyloidosis patients with renal involvement using time to event competing risk analysis at baseline, 3, 6 and 12 months after treatment. Only Palladini and Kastritis had a staging system and both predicted a higher risk of end stage renal disease (ESRD) in the stage III vs stage I patients but only the Palladini model was predictive for stage II patients. At 3 months, risk of ESRD was significantly higher for Palladini and ISA renal progression (hazard ratio [HR] 2.8 [95% CI: 1.5–5.3, p = .001] and 2.5 [CI: 1.4–4.6, p = .004, respectively]), but renal response was not significantly protective; conversely, the risk of ESRD was not significantly higher for the Kastritis renal progression, but was significantly protective for the Kastritis renal responders (HR 0.38 [95% CI: 0.17–0.84], p = .017). Both progression and response with ISA, Palladini and Kastritis criteria were predictive of ESRD at 6 months and 12 months. While the Palladini staging criteria at baseline, and the ISA and Palladini criteria for progression at 3 months performed better than the Kastritis criteria at baseline and 3 months post‐treatment, the Kastritis criteria performed better for response 3 months after treatment. All three sets of criteria performed well at and after 6 months post‐treatment. These differences are important when choosing endpoints for clinical trials.
Medical claims paid by workers' compensation insurance among US Medicare beneficiaries, 1999–2016
Authors: Kurth Laura , Casey Megan , Chin Brian , Mazurek Jacek M. , Schleiff Patricia , Halldin Cara , Blackley David J.
Published: January 2021

Background

Workers' compensation claims among Medicare beneficiaries have not been described previously. To examine the healthcare burden of work‐related injury and illness among Medicare beneficiaries, we assessed the characteristics, healthcare utilization, and financial costs among Medicare beneficiaries with claims for which workers' compensation was the primary payer.

Methods

We extracted final action fee‐for‐service Medicare claims from 1999 to 2016 where workers' compensation had primary responsibility for claim payment and beneficiary, claim type, diagnoses, and cost information from these claims.

Results

During 1999–2016, workers' compensation was the primary payer for 2,010,200 claims among 330,491 Medicare beneficiaries, and 58.7% of these beneficiaries had more than one claim. Carrier claims submitted by noninstitutional providers constituted the majority (94.5%) of claims. Diagnosis codes indicated 19.4% of claims were related to diseases of the musculoskeletal system and connective tissue and 12.9% were related to disease of the circulatory system. Workers' compensation insurance paid $880.4 million for these claims while Medicare paid $269.7 million and beneficiaries paid $37.4 million.

Conclusions

Workers' compensation paid 74% of the total amount to providers for these work‐related medical claims among Medicare beneficiaries. Claim diagnoses were similar to those of all workers' compensation claims in the United States. Describing these work‐related claims helps identify the healthcare burden due to occupational injury and illness among Medicare beneficiaries resulting from employment and identifies a need for more comprehensive collection and surveillance of work‐related medical claims.
Expansion of NEUROD2 phenotypes to include developmental delay without seizures
Authors: Mis Emily K. , Sega Annalisa G. , Signer Rebecca H. , Cartwright Tracy , Ji Weizhen , Martinez‐Agosto Julian A. , Nelson Stanley F. , Palmer Christina G. S. , Lee Hane , Mitzelfelt Thomas , Konstantino Monica ,   Undiagnosed Diseases Network, Jeffries Lauren , Khokha Mustafa K. , Marco Elysa , Martin Martin G. , Lakhani Saquib A.
Published: January 2021

De novo heterozygous variants in the brain‐specific transcription factor Neuronal Differentiation Factor 2 (NEUROD2) have been recently associated with early‐onset epileptic encephalopathy and developmental delay. Here, we report an adolescent with developmental delay without seizures who was found to have a novel de novo heterozygous NEUROD2 missense variant, p.(Leu163Pro). Functional testing using an in vivo assay of neuronal differentiation in Xenopus laevis tadpoles demonstrated that the patient variant of NEUROD2 displays minimal protein activity, strongly suggesting a loss of function effect. In contrast, a second rare NEUROD2 variant, p.(Ala235Thr), identified in an adolescent with developmental delay but lacking parental studies for inheritance, showed normal in vivo NEUROD2 activity. We thus provide clinical, genetic, and functional evidence that NEUROD2 variants can lead to developmental delay without accompanying early‐onset seizures, and demonstrate how functional testing can complement genetic data when determining variant pathogenicity.
Phenotypic spectrum associated with pathogenic mutation in the NRG1 gene in Acadian family
Authors: Bourcier Liane , Crapoulet Nicolas , Ouellette Rodney J. , Mallet Mathieu , Ben Amor Mouna
Published: January 2021

NRG1 is a gene that encodes for a protein that binds to a receptor of the tyrosine kinase family which is essential for the survival of the central nervous system development during embryogenesis. Mutation of the NRG1 gene causes aganglionosis, which leads to Hirschsprung disease. Two brothers of Acadian descent presented with a history of Hirschsprung disease, in association with other anomalies including congenital heart disease, learning difficulties, developmental issues, and hypopigmented hair patch. Molecular analysis in both siblings revealed a heterozygous pathogenic mutation in the NGR1 gene (c.235C>T [p.Arg79*]), that was inherited from an unaffected father. This family expands our knowledge about the phenotypic spectrum associated with pathogenic mutation in the NRG1 gene with intrafamilial variability and the likely reduced penetrance for the phenotypic expression.
Synthesis of Fully Substituted Oxazoles via an NFSI/KF‐Mediated Double Bond Cleavage‐Rearrangement Cascade
Authors: Wu Dan , Lu Yi , Hao Wen‐Juan , Tu Shu‐Jiang , Jiang Bo
Published: January 2021

An NFSI/KF‐mediated scission/recombination of C−C double bonds for [4+1] annulation is reported, leading to the efficient synthesis of a wide range of fully substituted oxazoles in good to excellent yields under mild redox‐neutral conditions. This methodology might open a new entry for the preparation of structurally applicable heterocyclic systems in a highly functional‐group‐compatible manner.
Recent Developments in Dehydrogenative Organic Transformations Catalyzed by Homogeneous Phosphine‐Free Earth‐Abundant Metal Complexes
Authors: Takallou Ahmad , Mesgarsaravi Niloofar , Beigbaghlou Somayyeh Sarvi , Sakhaee Nader , Halimehjani Azim Ziyaei
Published: January 2021

Stoichiometric amounts of various oxidants have long been employed for the oxidation of organic compounds. The major drawback of this method is the amount of toxic waste produced, which is in sharp contrast to principles of green chemistry. In catalytic dehydrogenation pathways, hydrogen carrier organic compounds (HCOCs) containing O−H, C−H, and N−H bonds can be transformed to their oxidized forms by removing two hydrogen atoms from the starting materials. Among the homogeneous transition metal‐ligand complexes that have been applied in a catalytic dehydrogenative approach, phosphine ligands have frequently been used. Over the past decades, phosphine‐free ligand systems have since been developed and implemented in various organic reactions to overcome the drawbacks associated with phosphine‐based catalysts. The aim of this review is to summarize the use of non‐phosphinic ligand‐metal complexes in organic transformations proceeding by a dehydrogenative pathway.
Ruthenium‐Catalyzed Synthesis of α‐Alkylated Ketones and Quinolines in an Aqueous Medium via a Hydrogen‐Borrowing Strategy Using Ketones and Alcohols
Authors: Verma Ashutosh , Hazra Susanta , Dolui Pritam , Elias Anil J.
Published: January 2021

Herein, we report a simple, efficient, and sustainable method for the synthesis of α‐alkylated ketones and quinolines using a hydrogen‐borrowing strategy, which has emerged as a greener alternative in organic transformation reactions. Synthesis of a range of α‐alkylated ketones and quinoline derivatives was achieved by using the water‐soluble [Ru(8‐AQ)Cl(p‐cym.)]+Cl− [Ru]‐1 (AQ=aminoquinoline) catalyst with water as the reaction medium. By adopting this strategy, we have synthesized α‐alkylated ketones and quinolines using ketones or secondary alcohols as starting materials and the primary alcohol as a green and naturally abundant alkylating agent.
Visible‐light‐mediated Synthesis of Bromo‐containing Azaspirotrienediones from N‐phenylpropynamides
Authors: Chen Yuan , Lu Fo‐Yun , Li Rui‐Xue , Guan Zhi , He Yan‐Hong
Published: January 2021

A visible‐light‐mediated reaction of N‐phenylpropynamides with diethyl 2,2‐dibromomalonate for the synthesis of bromo‐substituted azaspirotrienediones has been developed. This method allows the formation of C−Br, C−C and C=O bonds in one pot via a cascade radical addition/ipso‐cyclization/oxidation process. A possible radical mechanism involving single electron transfer and energy transfer processes is proposed based on control experiments, cyclic voltammetry determination and Stern‐Volmer quenching experiments.
Intersectionality and trauma analysis in bioarchaeology
Authors: Mant Madeleine , de la Cova Carlina , Brickley Megan B.
Published: January 2021

Intersectionality, the theory named by Kimberlé Crenshaw, outlines how multiple elements of an individual's social identity overlap to create and preserve societal inequalities and discrimination. Recently bioarchaeology's engagement with intersectionality has become increasingly explicit, as the field recognizes the lived experience of multiple axes of an individual's identity. Evidence of trauma can remain observable in an individual's skeleton for years, making it an ideal subject of study for intersectional analyses in bioarchaeology. Using contrasting case studies of two individuals who died in hospitals and were unclaimed after death, we explore the theoretical and methodological application of intersectionality to investigations of accidental and interpersonal trauma. Differences in identities and structural inequalities affect bone quality and health outcomes. As we demonstrate, a broken bone is the intersecting result of biological, histomorphological, sociocultural, and behavioral factors. This approach allows for a better acknowledgement of the inherent complexity of past lives, elevating and amplifying previously silenced voices. In this way, intersectionality in bioarchaeology demands social justice.
Multimodal Biomarkers Quantify Recovery in Autoimmune Autonomic Ganglionopathy
Authors: Koay Shiwen , Vichayanrat Ekawat , Bremner Fion , Panicker Jalesh N. , Lang Bethan , Lunn Michael P. , Watson Laura , Ingle Gordon T. , Hagen Ellen Merete , McNamara Patricia , Jacobson Leslie , Provitera Vincenzo , Nolano Maria , Vincent Angela , Mathias Christopher J. , Iodice Valeria
Published: January 2021

Objective

The objective of this study was to evaluate patients with ganglionic acetylcholine receptor antibody (gAChR‐Ab) positive autoimmune autonomic ganglionopathy using a multimodal testing protocol to characterize their full clinical phenotype and explore biomarkers to quantify immunotherapy response.

Methods

We conducted a cohort study of 13 individuals (7 women, 21–69 years of age) with autonomic failure and gAChR‐Ab >100 pM identified between 2005 and 2019. From 2018, all patients were longitudinally assessed with cardiovascular, pupillary, urinary, sudomotor, lacrimal and salivary testing, and Composite Autonomic Symptom Score (COMPASS‐31) autonomic symptom questionnaires. The orthostatic intolerance ratio was calculated by dividing change in systolic blood pressure over time tolerated on head‐up tilt. Eleven patients received immunotherapy.

Results

At first assessment, all 13 patients had cardiovascular and pupillary impairments, 7 of 8 had postganglionic sudomotor dysfunction, 9 of 11 had urinary retention and xeropthalmia, and 6 of 8 had xerostomia. After immunotherapy, there were significant improvements in orthostatic intolerance ratio (33.3 [17.8–61.3] to 5.2 [1.4–8.2], p = 0.007), heart rate response to deep breathing (1.5 [0.0–3.3] to 4.5 [3.0–6.3], p = 0.02), pupillary constriction to light (12.0 [5.5–18.0] to 19.0 [10.6–23.8]%, p = 0.02), saliva production (0.01 [0.01–0.05] to 0.08 [0.02–0.20] g/min, p = 0.03), and COMPASS‐31 scores (52 to 17, p = 0.03). Orthostatic intolerance ratio correlated with autonomic symptoms at baseline (r = 0.841, p = 0.01) and following immunotherapy (r = 0.889, p = 0.02). Immunofluorescence analyses of skin samples from a patient 32 years after disease onset showed loss of nerve fibers supplying the dermal autonomic adnexa and epidermis, with clear improvements following immunotherapy.

Interpretation

Patients with autoimmune autonomic ganglionopathy demonstrated objective evidence of widespread sympathetic and parasympathetic autonomic failure, with significant improvements after immunotherapy. Quantitative autonomic biomarkers should be used to define initial deficits, guide therapeutic decisions, and document treatment response. ANN NEUROL 2021;89:753–768
Reproduzierbarkeit in der elektroorganischen Synthese – Mythen und Missverständnisse
Authors: Beil Sebastian B. , Pollok Dennis , Waldvogel Siegfried R.
Published: January 2021

Die Verwendung von elektrischem Strom als spurenlosem Aktivator und Reagenz erlebt eine Renaissance in der organischen Synthesechemie. Diese nachhaltige Synthesemethode entwickelt sich zu einem hochaktuellen Thema in der modernen organischen Chemie. Forscher aus verschiedenen wissenschaftlichen Bereichen steigen in dieses interdisziplinäre Feld ein, was zu unterschiedlichen Parametern und Methoden der Experimentbeschreibungen führt. Die Variation in den berichteten Parametern kann zu Problemen bei der Reproduzierbarkeit elektroorganischer Synthesen führen. So sind z. B. Parameter wie die Stromdichte oder der Elektrodenabstand in manchen Fällen bedeutender als oft vermutet. Dieser Kurzaufsatz bietet Richtlinien für die Beschreibung elektrosynthetischer Daten an und räumt mit Mythen über diese Technik auf, wodurch die experimentellen Parameter vereinheitlicht werden sollen, um die Reproduzierbarkeit zu erleichtern.
1,2‐Aryl Migration Induced by Amide C−N Bond‐Formation: Reaction of Alkyl Aryl Ketones with Primary Amines Towards α,α‐Diaryl β,γ‐Unsaturated γ‐Lactams
Authors: Hu Rong , Tao Yigao , Zhang Xiaofeng , Su Weiping
Published: January 2021

Rearrangement reactions incorporated into cascade reactions play an important role in rapidly increasing molecular complexity from readily available starting materials. Reported here is a Cu‐catalyzed cascade reaction of α‐(hetero)aryl‐substituted alkyl (hetero)aryl ketones with primary amines that incorporates an unusual 1,2‐aryl migration induced by amide C−N bond formation to produce a class of structurally novel α,α‐diaryl β,γ‐unsaturated γ‐lactams in generally good‐to‐excellent yields. This cascade reaction has a broad substrate scope with respect to primary amines, allows a wide spectrum of (hetero)aryl groups to smoothly undergo 1,2‐migration, and tolerates electronically diverse α‐substituents on the (hetero)aryl ring of the ketones. Mechanistically, this 1,2‐aryl migration may stem from the intramolecular amide C−N bond formation which induces nucleophilic migration of the aryl group from the acyl carbon center to the electrophilic carbon center that is conjugated with the resulting iminium moiety.
A Chiral Pentafluorinated Isopropyl Group via Iodine(I)/(III) Catalysis
Authors: Meyer Stephanie , Häfliger Joel , Schäfer Michael , Molloy John J. , Daniliuc Constantin G. , Gilmour Ryan
Published: January 2021

An I(I)/(III) catalysis strategy to construct an enantioenriched fluorinated isostere of the iPr group is reported. The difluorination of readily accessible α‐CF3‐styrenes is enabled by the in situ generation of a chiral ArIF2 species to forge a stereocentre with the substituents F, CH2F and CF3 (up to 95 %, >20:1 vicinal:geminal difluorination). The replacement of the metabolically labile benzylic proton results in a highly preorganised scaffold as was determined by X‐ray crystallography (π→σ* and stereoelectronic gauche σ→σ* interactions). A process of catalyst editing is disclosed in which preliminary validation of enantioselectivity is placed on a structural foundation.
Na3SO4H—The First Representative of the Material Class of Sulfate Hydrides
Authors: Mutschke Alexander , Bernard Guy M. , Bertmer Marko , Karttunen Antti J. , Ritter Clemens , Michaelis Vladimir K. , Kunkel Nathalie
Published: January 2021

The first representative of a novel class of mixed‐anionic compounds, the sulfate hydride Na3SO4H, and the corresponding deuteride Na3SO4D were obtained from the solid‐state reaction of NaH or NaD with dry Na2SO4. Precise reaction control is required, because too harsh conditions lead to the reduction of sulfate to sulfide. A combined X‐ray and neutron diffraction study revealed that the compound crystallizes in the tetragonal space group P4/nmm with the lattice parameters a=7.0034(2) Å and c=4.8569(2) Å. The sole presence of hydride and absence of hydroxide ions is proven by vibrational spectroscopy and comparison with spectra predicted from quantum chemical calculations. 1H and 23Na MAS NMR spectra are consistent with the structure of Na3SO4H: a single 1H peak at 2.9 ppm is observed, while two peaks at 15.0 and 6.2 ppm for the inequivalent 23Na sites are observed. Elemental analysis and quantum chemical calculations further support these results.
Conformational Plasticity of Cyclic Ras‐Inhibitor Peptides Defines Cell Permeabilization Activity
Authors: Takeuchi Koh , Misaki Imai , Tokunaga Yuji , Fujisaki Miwa , Kamoshida Hajime , Takizawa Takeshi , Hanzawa Hiroyuki , Shimada Ichio
Published: January 2021

Cyclorasins 9A5 and 9A54 are 11‐mer cyclic peptides that inhibit the Ras‐Raf protein interaction. The peptides share a cell‐penetrating peptide (CPP)‐like motif; however, only cyclorasin 9A5 can permeabilize cells to exhibit strong cell‐based activity. To unveil the structural origin underlying their distinct cellular permeabilization activities, we compared the three‐dimensional structures of cyclorasins 9A5 and 9A54 in water and in the less polar solvent dimethyl sulfoxide (DMSO) by solution NMR. We found that cyclorasin 9A5 changes its extended conformation in water to a compact amphipathic structure with converged aromatic residues surrounded by Arg residues in DMSO, which might contribute to its cell permeabilization activity. However, cyclorasin 9A54 cannot adopt this amphipathic structure, due to the steric hindrance between two neighboring bulky amino‐acid sidechains, Tle‐2 and dVal‐3. We also found that the bulkiness of the sidechains at positions 2 and 3 negatively affects the cell permeabilization activities, indicating that the conformational plasticity that allows the peptides to form the amphipathic structure is important for their cell permeabilization activities.
Non‐Metal Ion Co‐Insertion Chemistry in Aqueous Zn/MnO2 Batteries
Authors: Wang Shuai , Yuan Zishun , Zhang Xu , Bi Songshan , Zhou Zhen , Tian Jinlei , Zhang Qichun , Niu Zhiqiang
Published: January 2021

The co‐insertion of dual ions can often offer enhanced electrochemical performance for the aqueous zinc batteries. Although the insertion of non‐metallic ions has been achieved in aqueous zinc batteries, the co‐insertion chemistry of non‐metallic cations is still a challenge. Here, a reversible H+/NH4+ co‐insertion/extraction mechanism was developed in an aqueous Zn/MnO2 battery system. The synergistic effect between the dual cations endows the aqueous batteries with the fast kinetics of ion diffusion and the reversible structure evolution of MnO2. As a result, the Zn/MnO2 battery displays excellent rate capability and cycling performance. This work will pave the way toward the design of aqueous rechargeable batteries with non‐metallic ions.
The Crucial Role of Local Excess Charges in Dendrite Growth on Lithium Electrodes
Authors: Santos Elizabeth , Schmickler Wolfgang
Published: January 2021

Much theoretical effort has been spent on the causes of dendrite formation in lithium metal batteries, but a decisive factor has been overlooked: Lithium is deposited on an electrode which carries a sizable negative charge, and this charge is not distributed homogeneously on the surface. We show by explicit model calculations that the excess charge accumulates on small protrusions and creates a strong electric field, which attracts the Li+ ions and induces further growth on the tip and finally the formation of dendrites. Even a small tip consisting of a few atoms will carry an excess charge of a tenth of a unit charge or more. In addition, the negative charge on the tips locally reduces the surface tension, which further fosters dendrite growth. The same principles can also explain dendrite formation on other metals with deposition potentials below the potential of zero charge.
Bio‐based sustainable films from the Algerian Opuntia ficus‐indica cladodes powder: Effect of plasticizer content
Authors: Makhloufi Nawal , Chougui Nadia , Rezgui Farouk , Benramdane Elias , Freire Carmen S. R. , Vilela Carla , Silvestre Armando J. D.
Published: January 2021

The present study investigated the fabrication and characterization of bio‐based sustainable films composed of a terrestrial plant raw material, namely Opuntia ficus‐indica (OFI) cladodes powder (CP) and a marine seaweed derivative, namely agar (A). The effect of glycerol concentration on the properties of the casted films was evaluated at four different contents, namely 30, 40, 50 and 60 wt%. The films present UV‐blocking properties, as well as moderate mechanical performance, thermal stability, and water vapor transmission rate (WVTR). The results point to an increase in thickness, elongation at break, moisture content, water solubility, and WVTR with increasing glycerol content. On the contrary, Young's modulus, tensile strength, and water contact angle decreased as glycerol concentration increased. The best combination is obtained for the film with 30% glycerol, based on an intermediate compromise between physical, mechanical, thermal, and barrier properties. All these outcomes express the potentiality of the powder obtained from grinding the OFI cladodes as raw material to produce low‐cost films for the development of sustainable packaging materials.
Super toughened and highly ductile PLA/TPU blend systems by in situ reactive interfacial compatibilization using multifunctional epoxy‐based chain extender
Authors: Kahraman Yusuf , Özdemir Burcu , Kılıç Volkan , Goksu Yonca Alkan , Nofar Mohammadreza
Published: January 2021

This study investigates the influence of using multifunctional epoxy Joncryl ADR 4468 chain extender (CE) on the properties of various polylactide (PLA)/thermoplastic polyurethane (TPU) (75 wt/25 wt) blend systems. The blends were based on two different TPU grades with ether‐ and ester‐based soft segment as the dispersed phase (i.e., TPUether and TPUester) and an amorphous and a semicrystalline PLA grades as the matrix (i.e., aPLA and scPLA). PLA appeared to be more compatible with the TPUester, which caused the enhancement of the impact strength and strain at break values of the blends more remarkably. The dynamic rheological experiments also confirmed that the CE revealed a better reactivity with TPUester than TPUether. This further enhanced the interfacial compatibility between the PLA and TPUester and thereby dramatically improved the impact strength and ductility of the PLA/TPUester blends, specifically those with 0.5 wt% CE. Meanwhile, aPLA as the matrix reflected the TPUs toughening effect more efficiently than scPLA. This was due to the possible shrinkage caused by the crystallization of scPLA matrix, which could deteriorate the interfacial interactions between the phases in the corresponding blends.
Radiation crosslinking of linear polyethyleneimine‐based nanoparticles grafted to poly(glycidyl methacrylate) via trimethylolpropane triacrylate as potential electronic packaging material
Authors: Ibrahim Saber , Lotfy Salah
Published: January 2021

Linear polyethyleneimine (L‐PEI)‐based nanoparticles were synthesized via hydrolysis of poly‐2‐methyl‐2‐oxazoline (PMeOx), which was prepared by cationic ring‐opening polymerization of the oxazoline five‐membered ring. Herein, a kinetic study of the ring‐opening polymerization reaction is discussed. The nuclear magnetic resonance spectrum of PMeOx verified the presence of repeating units and terminal groups in the polymer's structure. Molar ratios of PEI and PMeOx were characterized using size exclusion chromatography with low‐polydispersity polymer chains as the controlled polymerization reaction. PEI and PMeOx exhibited narrow particle size distribution with hydrodynamic radii of 89 and 67 nm, respectively, as determined via dynamic light scattering analysis. In addition, atomic forces and scanning electron microscopy were used to investigate the topography of the PEI thin films. Poly(glycidyl methacrylate) P(GMA) was grafted onto a PEI chain in the presence of trimethylolpropane triacrylate (TMPTA) as the crosslinking agent to synthesize the P(GMA–PEI–TMPTA) tripolymer via free radical polymerization using gamma irradiation. The thermal characterization of the P(GMA–PEI–TMPTA) tripolymer was conducted using thermogravimetric analysis and differential scanning calorimeter. Generally, the thermal stability of the P(GMA–PEI–TMPTA) tripolymer was improved at low‐glycidyl methacrylate concentrations. The prepared tripolymer could be used as effective packaging materials for electronics industries.
A comprehensive review of COVID‐19 in India: A frequent catch of the information
Authors: Shivangi  , Meena Laxman S.
Published: January 2021

The arrival of novel health crisis by a novel member of coronavirus group named as severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) by World Health Organization took the whole world in global emergency by affecting 206 countries. The virus infects 206 countries with 86,839,226 confirmed cases, 61,565,949 recoveries, and 1,876,243 deaths as on January 6, 2021. Evidence pointed out the fact that virus might first originated in bats in China and it took only 2 months to spread over almost every country of the world. SARS‐CoV‐2 belongs to beta coronavirus and is enveloped, positive sense, and single‐stranded RNA virus. The treatment would be difficult as SARS‐CoV‐2 is an RNA virus and thus the mutation rate is higher in comparison with the DNA viruses. The virus infection also leads to generation of effective protective immune response of tumor necrosis factor, interleukin (IL)‐1β, IL‐6, IL‐8, granulocyte colony‐stimulating factor, granulocyte‐macrophage colony‐stimulating factor, and so on that may help in virus elimination. The speed of the global spread of the current pandemic is of major concern and it has created a significant threat to economic and human health across the world. In India, the infection spreads with an infection and fatality rates of the disease are 1.7% and 2.8%, respectively. By this review, we want to emphasize the actual situation and major factors associated with COVID‐19 pandemic, its significance, destructions, important findings, treatments, and preventive measures taken by all nations to provide better cure without having much loss.
The interplay of ROS and the PI3K/Akt pathway in autophagy regulation
Authors: Kma Lakhan , Baruah Taranga Jyoti
Published: January 2021

Autophagy causes the breakdown of damaged proteins and organelles to their constituent components. The phosphatidylinositol 3‐kinase (PI3K) pathway played an important role in regulating the autophagic response of cells in response to changing reactive oxygen species (ROS) levels. The PI3K α catalytic subunit inhibits autophagy, while its β catalytic subunit promotes autophagy in response to changes in ROS levels. The downstream Akt protein acts against autophagy initiation in response to increases in ROS levels under nutrient‐rich conditions. Akt acts by activating a mechanistic target of the rapamycin complex 1 (mTORC1) and by arresting autophagic gene expression. The AMP‐activated protein kinase (AMPK) protein counteracts the Akt actions. mTORC1 and mTORC2 inhibit autophagy under moderate ROS levels, but under high ROS levels, mTORC2 can promote cellular senescence via autophagy. Phosphatase and tensin homolog (PTEN) protein are the negative regulators of the PI3K pathway, and it has proautophagic activities. Studies conducted on cells treated with flavonoids and ionizing radiation showed that the moderate increase in ROS levels in the flavonoid‐treated groups corresponded with higher PTEN levels and lowered Akt levels leading to a higher occurrence of autophagy. In contrast, higher ROS levels evoked by ionizing radiation caused a lowering of the incidence of autophagy.
Investigation of inhibition effect of butanol and water extracts of Matricaria chamomilla L. on angiotensin‐converting enzyme purified from human plasma
Authors: Bas Zehra , Turkoglu Vedat , Goz Yasar
Published: January 2021

Angiotensin‐converting enzyme (ACE) liable for the regulation of blood pressure was purified from human plasma by affinity chromatography. Impact of water and butanol extracts of Matricaria chamomilla L. on purity ACE was examined. ACE was purified using the affinity chromatography method. The enzyme activity was evaluated at 345 nm by a spectrophotometer. Extracts of M. chamomilla plant with butanol and water were prepared. Lisinopril was utilized as a specific inhibitor. ACE was purified 3,659‐fold from human plasma and the specific activity was 1,350 EU/mg protein. The molecular weight and purity of ACE were found by SDS‐PAGE and two bands of 60 and 70 kDa on the gel were detected. Water and butanol extracts of M. chamomilla demonstrated inhibitor impact on ACE activity. IC50 constants for water and butanol extracts of M. chamomilla were computed to be 1.292 and 0.353 mg/mL, respectively. The type of inhibition for whole inhibitors was identified as noncompetitive. IC50 and Ki constants for lisinopril were calculated to be 0.781 and 0.662 nM, respectively. These results indicate that butanol and water extracts of M. chamomilla may have an ACE inhibitor potential.
Asiaticoside inhibits renal fibrosis development by regulating the miR‐142‐5p/ACTN4 axis
Authors: Zhang Min , Liu Shuhuan , Fang Liming , Wang Gang , Yin Liping
Published: January 2021

Renal fibrosis results in the progressive renal dysfunction and leads to chronic kidney disease (CKD) and ultimately end‐stage renal disease. Asiaticoside was reported to regulate synaptopodin, desmin, nephrin, and podocin levels in adriamycin‐induced nephropathy of rats. In this study, we found out that asiaticoside inhibited renal fibrosis in vitro and in vivo. Additionally, miR‐142‐5p was upregulated in in vitro and in vivo models of CKD. MiR‐142‐5p promoted the levels of collagen‐I, collagen‐IV, and fibronectin proteins. Additionally, miR‐142‐5p overexpression partly rescued the protective effect of asiaticoside on renal fibrosis. Mechanistically, miR‐142‐5p inhibited ACTN4 levels by binding with its 3´untranslated region, and further reduced its translation. Treatment of asiaticoside decreased miR‐142‐5p levels and increased ACTN4 levels. Rescue assays revealed that ACTN4 overexpression partially rescued the effect of miR‐142‐5p on renal fibrosis. Asiaticoside mitigated renal fibrosis by regulating the miR‐142‐5p/ACTN4 axis. In conclusion, asiaticoside inhibits renal fibrosis by regulating the miR‐142‐5p/ACTN4 axis. This novel discovery suggested that asiaticoside may serve as a potential medicine for renal fibrosis improvement.
Beurteilung der Bauwerkszuverlässigkeit durch Bauwerksmonitoring
Authors: Herbrand Martin , Wenner Marc , Ullerich Christof , Rauert Tim , Zehetmaier Gerhard , Marx Steffen
Published: January 2021

Durch den schlechten Zustand vieler älterer Brücken und Änderungen in den Regelwerken ergeben sich häufig Defizite bei der Nachrechnung von Bestandsbrücken nach Nachrechnungsrichtlinie. Für den Fall, dass die erforderliche Bauwerkssicherheit nicht nachgewiesen werden kann, können Bauwerksmessungen zeitlich begrenzt oder als Dauermonitoring durchgeführt werden, um Erkenntnisse über die zeitlich veränderliche Beanspruchung zu gewinnen. Zentral hierfür ist die Ableitung von Zustandsindikatoren für das Bauwerk, die letztendlich den Handlungsbedarf für Betreiber und Ingenieure anzeigen. Im einfachsten Fall wird hierfür z. B. ein Ausnutzungsgrad ermittelt, der allerdings keinen Rückschluss auf das Risiko ermöglicht und streng genommen nur eine binäre Bewertung zulässt. In diesem Beitrag wird daher eine Vorgehensweise erläutert und am Beispiel der Hamburger Köhlbrandbrücke umgesetzt, die es erlaubt, einen Zuverlässigkeitsindex als zeitlich veränderlichen Zustandsindikator bezogen auf den Beulnachweis aus den dynamischen Monitoringdaten abzuleiten.