bluuebunny/crossref_metadata_2025 huggingface dataset:
Stable and Active Oxygen Reduction Catalysts with Reduced Noble Metal Loadings through Potential Triggered Support Passivation
Authors: Göhl Daniel , Rueß Holger , Schlicht Stefanie , Vogel Alexandra , Rohwerder Michael , Mayrhofer Karl J. J. , Bachmann Julien , Román‐Leshkov Yuriy , Schneider Jochen M. , Ledendecker Marc
Published: March 2020

The development of stable, cost‐efficient and active materials is one of the main challenges in catalysis. The utilization of platinum in the electroreduction of oxygen is a salient example where the development of new material combinations has led to a drastic increase in specific activity compared to bare platinum. These material classes comprise nanostructured thin films, platinum alloys, shape‐controlled nanostructures and core–shell architectures. Excessive platinum substitution, however, leads to structural and catalytic instabilities. Herein, we introduce a catalyst concept that comprises the use of an atomically thin platinum film deposited on a potential‐triggered passivating support. The model catalyst exhibits an equal specific activity with higher atom utilization compared to bulk platinum. By using potential‐triggered passivation of titanium carbide, irregularities in the Pt film heal out via the formation of insoluble oxide species at the solid/liquid interface. The adaptation of the described catalyst design to the nanoscale and to high‐surface‐area structures highlight the potential for stable, passivating catalyst systems for various electrocatalytic reactions such as the oxygen reduction reaction.
Chemical Route to Twisted Graphene, Graphene Oxide and Boron Nitride
Authors: Saraswat Aditi , Pramoda K. , Debnath Koyendrila , Servottam Swaraj , Waghmare Umesh V. , Rao C. N. R.
Published: March 2020

The recently discovered twisted graphene has attracted considerable interest. A simple chemical route was found to prepare twisted graphene by covalently linking layers of exfoliated graphene containing surface carboxyl groups with an amine‐containing linker (trans‐1,4‐diaminocyclohexane). The twisted graphene shows the expected selected area electron diffraction pattern with sets of diffraction spots out with different angular spacings, unlike graphene, which shows a hexagonal pattern. Twisted multilayer graphene oxide could be prepared by the above procedure. Twisted boron nitride, prepared by cross‐linking layers of boron nitride (BN) containing surface amino groups with oxalic acid linker, exhibited a diffraction pattern comparable to that of twisted graphene. First‐principles DFT calculations threw light on the structures and the nature of interactions associated with twisted graphene/BN obtained by covalent linking of layers.
Chemical Functionalisation of 2D Materials by Batch and Continuous Hydrothermal Flow Synthesis
Authors: Alli Uthman , Hettiarachchi Sunil J. , Kellici Suela
Published: March 2020

2D materials are single or few layered materials consisting of one or several elements with a thickness of a few nanometres. Their unique, tuneable physical and chemical properties including ease of chemical functionalisation makes this class of materials useful in a variety of technological applications. The feasibility of 2D materials strongly depends on better synthetic approaches to improve properties, increase performance, durability and reduce costs. As such, in the synthesis of nanomaterials, hydrothermal processes are widely adopted through a precursor–product synthesis route. This method includes batch or continuous flow systems, both employing water at elevated temperatures (above boiling point) and pressures to fine‐tune the physical, chemical, optical and electronic properties of the nanomaterial. Both techniques yield particles with different morphology, size and surface area due to different mechanisms of particle formation. In this Minireview, we present batch and continuous hydrothermal flow synthesis of a selection of 2D derivatives (graphene, MXene and molybdenum disulfide), their chemical functionalisation as an advantageous approach in exploring properties of these materials as well as the benefits and challenges of employing these processes, and an outlook for further research.
Dinuclear ZnII Complexes Exhibiting Thermally Activated Delayed Fluorescence and Luminescence Polymorphism
Authors: Xiong Jinfan , Li Kai , Teng Teng , Chang Xiaoyong , Wei Yaxiong , Wu Chao , Yang Chuluo
Published: March 2020

ZnII complexes exhibiting strong emission in the solid state remain scarce, and most of them exhibit only prompt fluorescence. Herein the synthesis, structures, and photoluminescence properties of two ZnII complexes containing new donor–acceptor ligands is reported. The new ZnII complexes have dinuclear structures in which each metal ion adopts a distorted square‐pyramidal geometry. The ZnII complexes show strong emission in the solid state with quantum yields up to 50 %. Variable‐temperature transient photoluminescence studies revealed an emission mechanism involving prompt and thermally activated delayed fluorescence (TADF). DFT calculations showed well‐separated HOMO and LUMO in the ground state and small excited singlet–triplet energy splitting, accounting for the TADF. The complexes also exhibit different emission colors in the as‐synthesized powder state and in single crystals, that is, they exhibit luminescence polymorphism. The single‐crystal emission is responsive to mechanical grinding and was characterized by powder XRD.
Novel, Dual Target‐Directed Annelated Xanthine Derivatives Acting on Adenosine Receptors and Monoamine Oxidase B
Authors: Kuder Kamil J. , Załuski Michał , Schabikowski Jakub , Latacz Gniewomir , Olejarz‐Maciej Agnieszka , Jaśko Piotr , Doroz‐Płonka Agata , Brockmann Andreas , Müller Christa E. , Kieć‐Kononowicz Katarzyna
Published: March 2020

Annelated purinedione derivatives have been shown to act as possible multiple‐target ligands, addressing adenosine receptors and monoaminooxidases. In this study, based on our previous results, novel annelated pyrimido‐ and diazepino[2,1‐f]purinedione derivatives were designed as dual‐target‐directed ligands combining A2A adenosine receptor (AR) antagonistic activity with blocking monoamine oxidase B. A library of 19 novel compounds was synthesized and biologically evaluated in radioligand binding studies at AR subtypes and for their ability to inhibit MAO‐B. This allowed 9‐(2‐chloro‐6‐fluorobenzyl)‐3‐ethyl‐1‐methyl‐6,7,8,9‐tetrahydropyrimido[2,1‐f]purine‐2,4(1H,3H)‐dione (13 e; Ki human A2AAR: 264 nM and IC50 human MAO‐B: 243 nM) to be identified as the most potent dual‐acting ligand from this series. ADMET parameters were estimated in vitro, and analysis of the structure‐activity relationships was complemented by molecular‐docking studies based on previously published X‐ray structures of the protein targets. Such dual‐acting ligands, by selectively blocking A2A AR, accompanied by the inhibition of dopamine metabolizing enzyme MAO‐B, might provide symptomatic and neuroprotective effects in, among others, the treatment of Parkinson disease
Aryloxy Triester Phosphoramidates as Phosphoserine Prodrugs: A Proof of Concept Study
Authors: Miccoli Ageo , Dhiani Binar A. , Thornton Peter J. , Lambourne Olivia A. , James Edward , Kadri Hachemi , Mehellou Youcef
Published: March 2020

The specific targeting of protein‐protein interactions by phosphoserine‐containing small molecules has been scarce due to the dephosphorylation of phosphoserine and its charged nature at physiological pH, which hinder its uptake into cells. To address these issues, we herein report the synthesis of phosphoserine aryloxy triester phosphoramidates as phosphoserine prodrugs that are enzymatically metabolized to release phosphoserine. This phosphoserine‐masking approach was applied to a phosphoserine‐containing inhibitor of 14‐3‐3 dimerization, and the generated prodrugs exhibited improved pharmacological activity. Collectively, this provided a proof of concept that the masking of phosphoserine with biocleavable aryloxy triester phosphoramidate masking groups is a viable intracellular delivery system for phosphoserine‐containing molecules. Ultimately, this will facilitate the discovery of phosphoserine‐containing small‐molecule therapeutics.
Enhanced Efficacy of Gefitinib in Drug‐Sensitive and Drug‐Resistant Cancer Cell Lines after Arming with a Singlet Oxygen Releasing Moiety
Authors: Huang Kunshan , Huo Beibei , Li Dongyao , Xue Jinping , Chen Juanjuan
Published: March 2020

Attractive results have been achieved with small‐molecule target‐based drugs in the anticancer field; however, enhancing their treatment effect and solving the problem of drug resistance remain key concerns worldwide. Inspired by the specific affinity of gefitinib for tumour cells and the strong oxidation capacity of singlet oxygen, we combined a chemically generated singlet oxygen moiety with the small‐molecule targeted drug gefitinib to improve its anticancer effect. We designed and synthesised a novel compound (Y5‐1), in which a small‐molecule targeted therapy agent (gefitinib) and a singlet oxygen (provided by an in vitro photodynamic reaction) thermally controlled releasing moiety are covalently conjugated. We demonstrated that the introduction of the singlet oxygen thermally controlled releasing moiety enhanced the anticancer activities of gefitinib. The results of this study are expected to provide a novel strategy to enhance the effect of chemotherapy drugs on drug‐resistant cell lines.
Synthesis and Biological Evaluation of Hapten‐Clicked Analogues of The Antigenic Peptide Melan‐A/MART‐126(27L)‐35
Authors: Tarbe Marion , Miles John J. , Edwards Emily S. J. , Miles Kim M. , Sewell Andrew K. , Baker Brian M. , Quideau Stéphane
Published: March 2020

A click‐chemistry‐based approach was implemented to prepare peptidomimetics designed in silico and made from aromatic azides and a propargylated GIGI‐mimicking platform derived from the altered Melan‐A/MART‐126(27L)‐35 antigenic peptide ELAGIGILTV. The CuI‐catalyzed Huisgen cycloaddition was carried out on solid support to generate rapidly a first series of peptidomimetics, which were evaluated for their capacity to dock at the interface between the major histocompatibility complex class‐I (MHC‐I) human leucocyte antigen (HLA)‐A2 and T‐cell receptors (TCRs). Despite being a weak HLA‐A2 ligand, one of these 11 first synthetic compounds bearing a p‐nitrobenzyl‐triazole side chain was recognized by the receptor proteins of Melan‐A/MART‐1‐specific T‐cells. After modification of the N and C termini of this agonist, which was intended to enhance HLA‐A2 binding, one of the resulting seven additional compounds triggered significant T‐cell responses. Thus, these results highlight the capacity of naturally circulating human TCRs that are specific for the native Melan‐A/MART‐126‐35 peptide to cross‐react with peptidomimetics bearing organic motifs structurally different from the native central amino acids.
Resolving Binding Events on the Multifunctional Human Serum Albumin
Authors: Wenskowsky Lea , Wagner Michael , Reusch Johannes , Schreuder Herman , Matter Hans , Opatz Till , Petry Stefan Matthias
Published: March 2020

Physiological processes rely on initial recognition events between cellular components and other molecules or modalities. Biomolecules can have multiple sites or mode of interaction with other molecular entities, so that a resolution of the individual binding events in terms of spatial localization as well as association and dissociation kinetics is required for a meaningful description. Here we describe a trichromatic fluorescent binding‐ and displacement assay for simultaneous monitoring of three individual binding sites in the important transporter and binding protein human serum albumin. Independent investigations of binding events by X‐ray crystallography and time‐resolved dynamics measurements (switchSENSE technology) confirm the validity of the assay, the localization of binding sites and furthermore reveal conformational changes associated with ligand binding. The described assay system allows for the detailed characterization of albumin‐binding drugs and is therefore well‐suited for prediction of drug‐drug and drug‐food interactions. Moreover, conformational changes, usually associated with binding events, can also be analyzed.
Promising progress from Healthy People 2020 and cancer incidence update
Authors: Ferris Robert L.
Published: March 2020

When we apply appropriate resources across the United States, we can measurably affect this terrible set of diseases by improving and expanding prevention and screening and by funding the basic and translational science that has given us today's real therapeutic gains from genomically targeted precision oncology and cancer immunotherapy, with the latter's attendant overall survival benefits.
Effects of the appearance care program for breast cancer patients receiving chemotherapy: A mixed method study
Authors: Ikeda Mari , Tamai Nao , Kanai Hisako , Osaka Misato , Kondo Kazuko , Yamazaki Takako , Sanada Hiromi , Kamibeppu Kiyoko
Published: March 2020

Background

Treatment of breast cancer entails surgery, often followed by chemotherapy. Alopecia is a major, intractable side effect with potentially profound impacts on appearance. We developed a nurse‐facilitated program targeting appearance‐related symptoms.

Aims

This study explored the effects of the appearance care program on quality of life (QOL). The program was delivered across three sessions, each involving personal reflections on appearance concerns, short lectures on skincare and makeover techniques, and small group discussions.

Method and Results

Seventy‐two women who attended the appearance care program were invited to participate. We employed a mixed‐method design combining quantitative and qualitative methods. QOL instruments were used to measure effects of the program at the first and final sessions and at a one‐month follow‐up. The qualitative data were collected as open‐ended notes regarding participants' perception of the program at the final session and at a one‐month follow‐up. Fifty‐seven women completed all three sessions. Of them, 55 participated in this study. Their mean age was 46.4 years; 39 (70.9%) had partners, and 34 (61.8%) had children. Most participants experienced hair loss at one‐month post‐program; however, cancer‐specific QOL improved after attending the program. Patients' experience of fatigue and weakness may explain observations of decreased physical well‐being. Emotional well‐being continued to increase 1 month following the program, while social and functional well‐being was consistent. Participants felt empowered by the information on skincare and cosmetic techniques and valued the intimate support from the group members facing similar circumstances.

Conclusions

This study showed that the appearance care program increased or maintained the well‐being of participants. Findings suggest the appearance care program which promoted group sharing experiences empowered participants and may have enhanced their coping strategies.
A noteworthy treatment of metastatic small‐cell lung cancer with afatinib, followed by subsequent development of rare metastatic lesions in the ascending and sigmoid colon
Authors: Hsiao Shih‐Chuan , Chen Yi‐Hsien , Lo Ching‐Chu , Lin Ching‐I
Published: March 2020

Background

Small‐cell lung cancer (SCLC) represents a group of highly fatal diseases with a tendency toward fast growth, early metastasis, and easy development of chemotherapy resistance. In the past 30 years, few advances have been made in the systemic treatment of SCLC, and cisplatin/etoposide has remained the standard of care for limited‐stage SCLC and, in combination with radiotherapy, extensive‐stage SCLC. The preferred metastatic sites of SCLC include the brain, liver, adrenal glands, bone, and bone marrow. However, bowel metastasis caused by SCLC is extremely rarely proved in patients while they are still alive (although autopsy studies suggest that silent metastases to the bowel are more common), and the standard treatment for bowel metastasis has never been reported. The mean time between the identification of gastrointestinal metastasis and mortality in patients with lung cancer is 100.6 days, with a range of 21–145 days.

Case

We report the case of a patient with extensive SCLC (including brain metastasis), in which exon 19 deletion of epidermal growth factor receptor (EGFR) was detected. She initially refused chemotherapy and cranial radiotherapy and instead only agreed to oral target therapy. The second‐generation EGFR‐tyrosine kinase inhibitor (TKI), afatinib, was administered to the patient, and partial remission, including smaller metastatic brain tumors, was noted. Even though the subsequent development of rare metastatic lesions in the ascending and sigmoid colon was proved by colonoscopic biopsies, the prolonged overall survival (400 days) without standard treatment was marked in this case.

Conclusion

The patient with extensive metastasis of SCLC did not receive standard systemic chemotherapy. Instead, she initially received second‐generation EGFR‐TKI afatinib alone and later on whole brain radiotherapy as well (3 weeks before she expired). The prolonged overall survival of 400 days was marked and is worthy of sharing and further investigation.
Multihop routing protocols on wireless ad hoc sensor networks with modified MAC layer and broadcasting scheme
Authors: Nguyen Tung T.
Published: March 2020

Most sensor devices are equipped with local batteries, placing a limitation on available energy, assuming that replacement of batteries is not feasible. This constraint limits the operation time of sensor networks. In many scenarios, sensors are operating in remote or dangerous areas, and it is impractical to replace or recharge the battery of the sensors. In some scenarios, such as machine monitoring or medical monitoring, it is more convenient to install new sensors than to replace the battery of the sensor nodes. The focus of this article is to design routing methods to achieve the maximum operation time of sensor networks (the number of rounds to transmit data) under the constraint of battery sources. Therefore, the main contribution of this research is not to change any characteristic of the network infrastructure, but to define the interactions between nodes to achieve better energy efficiency.
Reverse introduction of two‐ and six‐rowed barley lines from the United States into Egypt
Authors: Elbasyoni Ibrahim S. , Morsy Sabah M. , Naser Mahmoud , Ali Heba , Smith Kevin P. , Baenziger P. Stephen
Published: March 2020

In the current study, 248 two‐rowed and another 253 six‐rowed spring barley (Hordeum vulgare L.) breeding lines from several US barley breeding programs were evaluated in multiple locations in Egypt to select for potentially adapted lines. The introduced plant materials were planted in two locations during three growing seasons (2015, 2016, and 2017). The focus of the first growing season was to increase available seeds and collect preliminary observations. During the second and third growing seasons, the advanced plant materials and local check cultivars were planted in an incomplete block design in two replicates within three locations. Grain yield, leaf rust, number of days to flowering, and plant height were measured. Based on grain yield production, the top 94 lines from the two‐rowed and 100 from the six‐rowed barley lines were selected and advanced for further evaluation in 2017. The introduced materials contained several lines that consistently outperformed the check cultivars. Therefore, these lines could be used as parents to improve barley production and enhance genetic diversity or be directly released as cultivars after appropriate testing in Egypt.
Four‐port shared rectangular radiator with defected ground for wireless application
Authors: Chouhan Sanjay , Malviya Leeladhar
Published: March 2020

In this research work, a modified shared rectangular radiator is proposed for 5.7‐GHz wireless application using multiple cuts and partially stepped ground. The shared design requires no isolating structure to decouple the ports. The proposed shared geometry produces >13 dB isolation in the 4.4‐ to 6.4‐GHz operating band. The gain varies from 3.0 to 6.2 dBi, and radiation efficiency is >70 % in the band. The mutual coupling among the port is reduced by orthogonal arrangement of ports, and envelope correlation coefficient (ECC) is <0.04 in the presented band. Apart from this, isolation in the proposed shared radiator is enhanced by additional multiple cuts with stepped ground. The indoor‐outdoor suitability of multiple input multiple output (MIMO) antenna for isotropic and Gaussian medium is checked by mean effective gain (MEG) and specific absorption rate (SAR). The presented results of MEG and SAR fulfill the required safety norms as per the ITU for different environments.
Preparation, characterization, and sonodynamic antitumor effect of the folate receptor targeted FA‐EN‐β‐CD containing hematoporphyrin in vitro
Authors: Wang Chuanjin , Du Fuqiang
Published: March 2020

To improve water solubility, reduce phototoxicity and increase the tumor‐targeting ability of hematoporphyrin (Hp) as a sonosensitizer for sonodynamic therapy under ultrasonic conditions, a novel folate receptor (FR)‐targeted, folate‐conjugated ethylenediamine‐β‐cyclodextrin (FA‐EN‐β‐CD) containing Hp (FA‐EN‐β‐CD‐Hp) was constructed. β‐Cyclodextrin containing Hp (β‐CD‐Hp) was also established as a nontargeted control. The inclusion efficiencies of Hp in FA‐EN‐β‐CD‐Hp and β‐CD‐Hp were determined to be 90.4 ± 2.7% (wt/wt) and 92.5 ± 3.4% (wt/wt), respectively. Growth inhibition rates in HepG‐2 cells in vitro were assessed upon ultrasound exposure. The results indicated that the growth inhibition rates of FA‐EN‐β‐CD‐Hp, β‐CD‐Hp, and F‐Hp (Hp: 150 μg/ml) reached 96.4 ± 3.6%, 53.4 ± 3.4%, and 48.2 ± 2.8%, respectively. These results indicated that FA‐EN‐β‐CD‐Hp is a promising drug delivery system in the field of sonodynamic cancer therapy.
Evolution of major histocompatibility complex class I genes in the sable Martes zibellina (Carnivora, Mustelidae)
Authors: Zhao Baojun , Zhang Xue , Li Bo , Du Pengfei , Shi Lupeng , Dong Yuehuan , Gao Xiaodong , Sha Weilai , Zhang Honghai
Published: March 2020

The molecules encoded by major histocompatibility complex (MHC) genes play an essential role in the adaptive immune response among vertebrates. We investigated the molecular evolution of MHC class I genes in the sable Martes zibellina. We isolated 26 MHC class I sequences, including 12 putatively functional sequences and 14 pseudogene sequences, from 24 individuals from two geographic areas of northeast China. The number of putatively functional sequences found in a single individual ranged from one to five, which might be at least 1–3 loci. We found that both balancing selection and recombination contribute to evolution of MHC class I genes in M. zibellina. In addition, we identified a candidate nonclassical MHC class I lineage in Carnivora, which may have preceded the divergence (about 52–57 Mya) of Caniformia and Feliformia. This may contribute to further understanding of the origin and evolution of nonclassical MHC class I genes. Our study provides important immune information of MHC for M. zibellina, as well as other carnivores.
Insulin/carbohydrates ratio during the first 6‐month therapy with insulin degludec in a paediatric population with type 1 diabetes previously treated with insulin glargine. An observational longitudinal study
Authors: Tumini Stefano , Iacono Olimpia , Comegna Laura , Fioretti Elisabetta , Guidone Paola , Levantini Gabriella , Panichi Daniele , Catenaro Milena , Rossi Ilaria , Amaro Flavia , Graziano Giusi , Rossi Maria Chiara , Cipriano Paola
Published: March 2020

Background

No data exist about the changes induced by the transition from first‐generation long‐acting insulins to second‐generation long‐acting analogues in the paediatric population.

Objective

To assess changes in insulin/carbohydrate ratio (I:CHO) after the first 6 months of degludec therapy in a paediatric population with type 1 diabetes previously treated with glargine U100.

Subjects

All patients treated with degludec under routine clinical practice conditions were retrospectively analysed.

Methods

Nonprofit observational retrospective study. Changes during the follow‐up in mean CHO/I ratio were assessed using longitudinal linear models for repeated measures. Rate of hypoglycaemia, ketoacidosis and adverse events was evaluated.

Results

Overall, 51 children (mean age 13.8 ± 4.6 years; mean diabetes duration 5.8 ± 3.9 years) started therapy with degludec in the period between April 2017 and April 2018. I:CHO ratio before starting degludec therapy significantly differed among the three meals, being the lowest at breakfast and the highest at dinner. After introducing degludec, I:CHO ratio at lunch (−1.29 95% CI −2.02;−0.57) and at dinner (−3.08 95% CI −4.35;−1.8) significantly decreased, while it slightly increased at breakfast (+1.37 95% CI 0.47;2.28). No episodes of severe hypoglycaemia, ketoacidosis and adverse event were recorded during 6 months.

Conclusions

Our data show that the use of degludec is associated with a significant change in the I:CHO ratio at the different meals compared to the previous glargine therapy. This could derive from the flat and prolonged pharmacokinetic profile of degludec. This has important clinical implications for daily insulin dose adjustments.
Non‐invasive telemedical care in heart failure patients and stroke: post hoc analysis of TIM‐HF and TIM‐HF2 trials
Authors: Tütüncü Serdar , Honold Marcus , Koehler Kerstin , Deckwart Oliver , Koehler Friedrich , Haeusler Karl Georg
Published: March 2020

Aims

Patients with chronic heart failure (CHF) have an increased risk of ischaemic stroke. We aimed to identify the incidence rate and factors associated with ischaemic stroke or transient ischaemic attack (TIA) in CHF patients as well as the impact of non‐invasive telemedical care (NITC) on acute stroke/TIA.

Methods and results

We retrospectively analysed baseline characteristics of 2248 CHF patients enrolled to the prospective multicentre Telemedical Interventional Monitoring in Heart Failure study (TIM‐HF) and Telemedical Interventional Management in Heart Failure II study (TIM‐HF2), randomizing New York Heart Association (NYHA) II/III patients 1:1 to NITC or standard of care. Hospitalizations due to acute ischaemic stroke or TIA during a follow‐up of 12 months were analysed. Old age, hyperlipidaemia, lower body mass index, and peripheral arterial occlusive disease (PAOD) were independently associated with present cerebrovascular disease on enrolment. The stroke/TIA rate was 1.5 per 100 patients‐years within 12 months after randomization (n = 32, 1.4%). Rate of stroke/TIA within 12 months was in the intervention group similar compared with the control group (50.0% vs. 49.8%; P = 0.98) despite that the rate of newly detected atrial fibrillation (AF) was higher in the intervention group (14.1% vs. 1.6%; P < 0.001). A history of PAOD (OR 2.7, 95% CI 1.2–6.2; P = 0.02) and the highest tertile (OR 3.0, 95% CI 1.1–8.3) of N‐terminal pro‐brain natriuretic peptide (NT‐proBNP) on enrolment were associated with stroke/TIA during follow‐up. In patients who suffered acute stroke or TIA during follow‐up, echocardiography was part of the diagnostic workup in only 56% after hospital admission.

Conclusions

Annual rate of ischaemic stroke/TIA in NYHA II/III patients is low but higher in those with elevated NT‐proBNP levels and history of PAOD at baseline. NITC showed no impact on the stroke rate during 1 year follow‐up despite a significantly higher rate of newly detected AF. Irrespective of known CHF, echocardiography was often missing during in‐hospital diagnostic workup after acute stroke/TIA.
Metal Complexes Bearing Dianionic Trityl/Aryloxide Ligands: Rational Synthesis, Structural Diversity, and Redox Properties
Authors: Huang Zhuanying , Zhong Tingshan , Feng Tangbiao , Zhao Jixing , Zhong Hailan , Lei Hao
Published: March 2020

Lithium complexes containing bidentate dianionic trityl/aryloxide ligands, Li2[ROC](Et2O)n ([ROC]2– = [κ2‐O,C‐OC6H2‐2‐C(3,5‐R2C6H3)2‐4,6‐tBu2]2–; 2a (R = H, n = 1) and 2b (R = Me, n = 0)) were synthesized through double metalation of ortho‐benzhydryl phenols with nBuLi. Similarly, sodium compound Na2[HOC](THF)2.5 (3a) was obtained when phenol H2[HOC] (1a) was treated with two equiv. of nBuLi/NaOtBu. The lithium compounds were employed for the preparation of other metal complexes supported by [ROC]2– ligands, i.e. {Zn[ROC](THF)}2 (R = H (4a) or Me (4b)), Sn[HOC]2 (5a) and Cp*Ir[MeOC] (6b, Cp* = η5‐C5Me5), by salt metathesis reactions with metal halides. The solid‐state structures of all metal complexes were established by X‐ray crystallography. The nuclearity of these metal complexes and the coordination fashion of the [ROC]2– ligands were found to be highly dependent on the identity of metal centers. Additionally, compound 2a was found to be facilely oxidized, as revealed by both electrochemical and reactivity study.
Palladium‐Based Catalysts Supported by Unsymmetrical XYC–1 Type Pincer Ligands: C5 Arylation of Imidazoles and Synthesis of Octinoxate Utilizing the Mizoroki–Heck Reaction
Authors: Maji Ankur , Singh Ovender , Singh Sain , Mohanty Aurobinda , Maji Pradip K. , Ghosh Kaushik
Published: March 2020

A series of new unsymmetrical (XYC–1 type) palladacycles (C1–C4) were designed and synthesized with simple anchoring ligands L1–4H (L1H = 2‐((2‐(4‐methoxybenzylidene)‐1‐phenylhydrazinyl)methyl)pyridine, L2H = N,N‐dimethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐ylmethyl)hydrazono)methyl)aniline, L3H = N,N‐diethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐ylmethyl)hydrazono)methyl) aniline and L4H = 4‐(4‐((2‐phenyl‐2‐(pyridin‐2‐ylmethyl)hydrazono) methyl)phenyl)morpholine H = dissociable proton). Molecular structure of catalysts (C1–C4) were further established by single X‐ray crystallographic studies. The catalytic performance of palladacycles (C1–C4) was explored with the direct Csp2–H arylation of imidazoles with aryl halide derivatives. These palladacycles were also applied for investigating of Mizoroki–Heck reactions with aryl halides and acrylate derivatives. During catalytic cycle in situ generated Pd(0) nanoparticles were characterized by XPS, SEM and TEM analysis and possible reaction pathways were proposed. The catalyst was employed as a pre‐catalyst for the gram‐scale synthesis of octinoxate, which is utilized as a UV‐B sunscreen agent.
Enantioselective N‐Acylation of Biginelli Dihydropyrimidines by Oxidative NHC Catalysis
Authors: Brandolese Arianna , Ragno Daniele , Leonardi Costanza , Di Carmine Graziano , Bortolini Olga , De Risi Carmela , Massi Alessandro
Published: March 2020

The oxidative N‐acylation reaction of 3,4‐dihydropyrimidin‐2‐(1H)‐ones (DHPMs) with enals and N‐heterocyclic carbene (NHC) catalysts is described. The reaction proceeds in the presence of quinone oxidant without additional acyl transfer agents and in the asymmetric variant produces pharmaceutically relevant N3‐acylated products with good‐to‐moderate enantioselectivity.
On the Necessity of One‐Pot Tautomer Trapping in Asymmetric Michael Reactions of Arylideneisoxazol‐5‐ones
Authors: Macchia Antonio , Cuomo Valentina Dafnae , Di Mola Antonia , Pierri Giovanni , Tedesco Consiglia , Palombi Laura , Massa Antonio
Published: March 2020

Herein we report the first asymmetric Michael reaction of arylidene‐isoxazol‐5‐one with 1,3‐diesters. Despite complex tautomer equilibria of the obtained Michael adducts, the one‐pot entrapping strategy by the aid of different electrophiles/protecting groups led to the selective isolation of diverse N‐substituted isoxazol‐5‐ones in very high overall yield and good enantioselectivity. Asymmetric three components Michael/electrophilic tautomer‐entrapping and four‐component Knoevenagel/Michael/electrophilic‐tautomer‐entrapping methodologies have also been developed. The enantiopurity of several final products was further increased after crystallization, up to > 99.9:0.1 er in good overall yields.
A Novel Ternary Graphene‐based Nanocomposite Modified Electrode for Acetaminophen Detection
Authors: Singh Manorama , Sahu Anjumala , Singh Puneet K. , Verma Fooleswar , Rai Ankita , Rai Vijai K.
Published: March 2020

Herein, design and synthesis of ternary gold nanoparticles@ sulfourea‐functionalized reduced graphene oxide (Gold‐NPs@SFG) is reported. It involves interaction of ‘sulfourea’ to the graphene sheets via amidation of edged carboxyls of graphene oxide with N‐terminals of sulfourea followed by association of Gold‐NPs. Sulfourea not only reduced the graphene oxide but interestingly, it is functionalized to graphene sheets via carbodiimide covalent junctions, which gives it local effect to increase the active surface area and excellent electrocatalytic properties. The prepared nanocomposite was characterized with SEM, TEM, FTIR, Raman, XRD, XPS and CV. Gold‐NPs@SFG was found to be more efficient electrocatalyst for the electrocatalytic oxidation of a drug ‘Acetaminophen’ using differential pulse voltammetry and it was employed as a highly sensitive and selective electrochemical sensor for the quantification of ‘Acetaminophen’ with the detection limit of 0.09 μM in the wide linear range of 1.2 to 300 μM.
Electrocatalytic conversion of lithium polysulfides by highly dispersed ultrafine Mo2C nanoparticles on hollow N‐doped carbon flowers for Li‐S batteries
Authors: Razaq Rameez , Zhang Nana , Xin Ying , Li Qian , Wang Jin , Zhang Zhaoliang
Published: March 2020

The significant challenge in exploring novel nanostructured sulfur host materials for Li‐S batteries is to simultaneously mitigate the notorious shuttle effect and catalytically enhance the redox kinetics of lithium polysulfides (LPSs). Herein, a novel ultrafine Mo2C nanoparticles uniformly distributed on 2D nanosheet‐assembled 3D hollow nitrogen‐doped carbon flowers (HNCFs) is designed. The Mo2C/HNCFs architecture with unique flower‐like morphologies not only efficiently suppressed the aggregation of 2D nanosheets but also highly distributed the ultrafine Mo2C nanoparticles that act as catalytic active sites for efficient adsorption and conversion of LPSs. Furthermore, the 3D hierarchical arrangement can afford ample internal space to accommodate sulfur species, large volume expansion, 3D electron pathway, and physical/chemical blockage of LPSs to reduce the loss of active materials. The Mo2C/HNCFs composite exhibits a high rate capability, unprecedented capacity retention of 92% over 100 cycles at 0.5 C placing Mo2C/HNCFs one of the best LPSs adsorbents and electrocatalysts.

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Dynamic analysis of track nonlinear energy sinks subjected to simple and stochastice excitations
Authors: Wang Jingjing , Wang Bin , Wierschem Nicholas E. , Spencer Billie F.
Published: March 2020

Track nonlinear energy sinks (track NESs) have been shown to be an effective and applicable strategy to mitigate structural response in recent years. However, previous studies on track NESs has mainly focused on demonstrating the benefits of track NESs through numerical simulations and experiments, with relatively little attention paid to the analytical understanding of the unique dynamics of track NESs. This study analyzes the responses of a track NES when subjected to impulsive and harmonic excitations by the harmonic balance method. Special attention is given to the cause and effect of the peaking behavior that is a prominent characteristic of the track NES's restoring force–displacement relationship. Analytical results reveal that the special energy–frequency characteristics of track NESs can be, at times, utilized to enhance the energy robustness that is absent in the conventional cubic NESs. Based on the analytical response expression, an equivalent linearization method (ELM) for the track NESs is developed for stochastic analysis. This ELM is numerically validated on the systems with strong nonlinearities. Stochastic optimization built on the ELM is performed to obtain design parameters of the track NES that can lead to minimum response variances of the primary structure. In particular, the proposed optimization procedure can be applied to seismic optimum design in which the seismic excitations are modeled as filtered white‐noise ground motions. The analytical techniques provided in this study lay the groundwork for the practical implementation of track NESs as a robust and effective control strategy for engineering structures.
Channel and vegetation recovery from dredging of a large river in the Gulf coastal plain, USA
Authors: Mossa Joann , Chen Yin‐Hsuen , Kondolf G. Mathias , Walls Scott Porter
Published: March 2020

Anthropogenic impacts in large rivers are widely studied, but studies of recovery once a disturbance has stopped are uncommon. This study examines the biogeomorphic recovery of a 40‐km river corridor on the mid‐Apalachicola River, Florida following the cessation of dredging, disposal, and snag removal in 2002. This failed navigation project resulted in vegetation losses (~166 ha between 1941 and 2004), river widening, and increased point bar areas. We used paired sets of imagery for a 10‐year period during the recovery process at two different flow levels to assess sand bar change, land cover change, and their spatial variations.

Most large sand bars decreased significantly in area due to growth of pioneer species, typically from the bankside of the bar. Mean bar area shrank 0.17 and 0.20 ha for the 30th and 1st percentile flows, respectively. For the entire study area, both water‐level comparisons showed gains in vegetation (23.36 and 15.83 ha), compensated by losses in the extent of water (16.83 and 8.55 ha) and sand bar losses (6.53 and 7.28 ha). Overall, these gains during the 10‐year passive recovery period are equivalent to ~15% of the vegetation losses that resulted from the navigational dredging.

As found in other studies, most of the pioneer vegetation grew approximately 2 m relative elevation above the low‐water surface. The initial length of the tree line and the area of herbaceous growth both had a significant and positive relationship with the area of new vegetation growth over the study interval. As parts of the river are healing, reduced channel capacity from narrowing and tree growth will benefit the floodplain. As elsewhere, understanding of a river's biogeomorphology, hydrology, and disturbance history can help in selecting appropriate recovery metrics to further advance the understanding and management of disturbed floodplains. © 2020 John Wiley & Sons, Ltd.
Effects of Formalin Fixation on Trace Element Concentrations in Bottlenose Dolphin (Tursiops truncatus) Tissues
Authors: McCormack Meaghan A. , Jackson Brian P. , Dutton Jessica
Published: March 2020

Odontocetes are considered ideal sentinel species to monitor environmental trace element concentrations. Although frozen tissues are preferable for trace element analysis, formalin-fixed tissues are often the only samples available; however, it is uncertain whether formalin fixation alters tissue trace element concentrations. To explore whether formalin-fixed tissues could be utilized for toxicology studies, concentrations of 14 trace elements (arsenic [As], cadmium, cobalt, chromium, copper, iron, mercury, manganese, nickel, lead, selenium, tin, vanadium, and zinc [Zn]) were measured in frozen and formalin-fixed bottlenose dolphin (Tursiops truncatus) tissues following short-term (6 wk; tissues: blubber, liver, and lung) and long-term preservation (3–7 yr; tissues: blubber, brain, kidney, liver, lung, and skin) using inductively coupled plasma mass spectrometry. Following both short-term and long-term preservation, there were significant differences in tissue trace element concentrations between preservation methods. Some trace elements were found in greater concentrations in frozen tissues compared with formalin-fixed tissues, suggesting leaching (e.g., mean As concentrations were between 1.4 and 7.6 times greater in frozen tissues). In contrast, other trace elements were found in greater concentrations in formalin-fixed tissues compared with frozen tissues, suggesting contamination (e.g., mean Zn concentrations were up to 8.7 times higher in some formalin-fixed tissues). Our results suggest that it may be possible to account for the effects of formalin fixation for some trace elements, but leaching and contamination should be carefully considered. Environ Toxicol Chem 2020;39:1149–1164. © 2020 SETAC
Epigenetic regulation for acquiring glial identity by neural stem cells during cortical development
Authors: Nakagawa Takumi , Wada Yoshikuni , Katada Sayako , Kishi Yusuke
Published: March 2020

The nervous system consists of several hundred neuronal subtypes and glial cells that show specific gene expression and are generated from common ancestors, neural stem cells (NSCs). As the experimental techniques and molecular tools to analyze epigenetics and chromatin structures are rapidly advancing, the comprehensive events and genome‐wide states of DNA methylation, histone modifications, and chromatin accessibility in developing NSCs are gradually being unveiled. Here, we review recent advances in elucidating the role of epigenetic and chromatin regulation in NSCs, especially focusing on the acquisition of glial identity and how epigenetic regulation enables the temporal regulation of NSCs during murine cortical development.
In vivo silencing of miR‐125a‐3p promotes myelin repair in models of white matter demyelination
Authors: Marangon Davide , Boda Enrica , Parolisi Roberta , Negri Camilla , Giorgi Corinna , Montarolo Francesca , Perga Simona , Bertolotto Antonio , Buffo Annalisa , Abbracchio Maria P. , Lecca Davide
Published: March 2020

In the last decade, microRNAs have been increasingly recognized as key modulators of glial development. Recently, we identified miR‐125a‐3p as a new player in oligodendrocyte physiology, regulating in vitro differentiation of oligodendrocyte precursor cells (OPCs). Here, we show that miR‐125a‐3p is upregulated in active lesions of multiple sclerosis (MS) patients and in OPCs isolated from the spinal cord of chronic experimental autoimmune encephalomyelitis (EAE) mice, but not in those isolated from the spontaneously remyelinating corpus callosum of lysolecithin‐treated mice. To test whether a sustained expression of miR‐125a‐3p in OPCs contribute to defective remyelination, we modulated miR‐125a‐3p expression in vivo and ex vivo after lysolecithin‐induced demyelination. We found that lentiviral over‐expression of miR‐125a‐3p impaired OPC maturation, whereas its downregulation accelerated remyelination. Transcriptome analysis and luciferase reporter assay revealed that these effects are partly mediated by the direct interaction of miR‐125a‐3p with Slc8a3, a sodium–calcium membrane transporter, and identified novel candidate targets, such as Gas7, that we demonstrated necessary to correctly address oligodendrocytes to terminal maturation. These findings show that miR‐125a‐3p upregulation negatively affects OPC maturation in vivo, suggest its role in the pathogenesis of demyelinating diseases and unveil new targets for future promyelinating protective interventions.
A toolbox for brain network construction and classification (BrainNetClass)
Authors: Zhou Zhen , Chen Xiaobo , Zhang Yu , Hu Dan , Qiao Lishan , Yu Renping , Yap Pew‐Thian , Pan Gang , Zhang Han , Shen Dinggang
Published: March 2020

Brain functional network has been increasingly used in understanding brain functions and diseases. While many network construction methods have been proposed, the progress in the field still largely relies on static pairwise Pearson's correlation‐based functional network and group‐level comparisons. We introduce a “Brain Network Construction and Classification (BrainNetClass)” toolbox to promote more advanced brain network construction methods to the filed, including some state‐of‐the‐art methods that were recently developed to capture complex and high‐order interactions among brain regions. The toolbox also integrates a well‐accepted and rigorous classification framework based on brain connectome features toward individualized disease diagnosis in a hope that the advanced network modeling could boost the subsequent classification. BrainNetClass is a MATLAB‐based, open‐source, cross‐platform toolbox with both graphical user‐friendly interfaces and a command line mode targeting cognitive neuroscientists and clinicians for promoting reliability, reproducibility, and interpretability of connectome‐based, computer‐aided diagnosis. It generates abundant classification‐related results from network presentations to contributing features that have been largely ignored by most studies to grant users the ability of evaluating the disease diagnostic model and its robustness and generalizability. We demonstrate the effectiveness of the toolbox on real resting‐state functional MRI datasets. BrainNetClass (v1.0) is available at https://github.com/zzstefan/BrainNetClass.
An improved weighted fuzzy CREAM model for quantifying human reliability in subway construction: Modeling, validation, and application
Authors: Wang Ning , Du Xiuli , Zhang Mingju , Xu Chengshun , Lu Xinyue
Published: March 2020

On construction sites, there are many catastrophic accidents induced by human error. The fuzzy cognitive reliability and error analysis method (CREAM) is an effective method for assessing human error hazards in such a context. However, deficiencies regarding the aspects of reasonably considering the input weight, evaluation of common performance conditions (CPCs), and the rule‐based approach for fuzzy illation are frequently encountered. This paper provides an improved weighted fuzzy CREAM model. First, the reasonable weight of the CPCs is obtained by using multiple correlation analysis and evidence theory. Second, the specific evaluation rules for CPCs are established based on Chinese codes, and the membership function for each CPC level is obtained by a statistical method. The discrete basic diagram for the control mode is then transformed into a continuous fuzzy rule‐based model. On that basis, the rationality and reliability of the model are verified by four axioms. The method that introduces the weights into the calculation of the expected effects of CPCs and the reasoning of human error probability (HEP) can help evaluate the effectiveness of CPCs on human performance. The model is sensitive to the minor alterations of CPC scores and weights; the sufficiency of the data utilization and the solution domain are also verified. An exemplified application shows the rationality and validity of the new weighted fuzzy CREAM for shield tunneling human reliability analysis. This model also provides essential HEP data that can be used in hazard analysis in other engineering fields.