bluuebunny/crossref_metadata_2025 huggingface dataset:
Pd based on 2‐Aminopyrimidine and 1H‐benzo[d]imidazol‐2‐amine functionalizedFe3O4 nanoparticles as novel recyclable magnetic nanocatalysts for Ullmann coupling reaction
Authors: Chen Jin , Dai Linfang , Li Jiayu , Mohammadnia Majid
Published: May 2020

In this study, Pd based on 2‐Aminopyrimidine and 1H‐benzo[d]imidazol‐2‐amine functionalized Fe3O4 magnetic nanoparticles [(Pd‐APM‐PSi‐Fe3O4) and (Pd‐BIA‐PSi‐Fe3O4)] was designed and used for the synthesis of di aryl ether by Ulmann cross‐coupling reactions. Ulmann reaction performed with mixing of the arylhalides and phenol derivatives in DMF solvent. The prepared catalysts were characterized with various analytical techniques such as FT‐IR, XRD, TGA, SEM, TEM, EDX, ICP and VSM. Pd‐APM‐PSi‐Fe3O4 and Pd‐BIA‐PSi‐Fe3O4 catalysts demonstrated good to excellent yields catalytic efficiency for Ulmann reactions in comparison with to commercial palladium catalysts. The catalyst is easily recycled and reused without loss of the catalytic activity. The combined merits of reusable catalyst conditions make the condensation with safe operation, no leaching of pd into environment, low pollution, rapid access to products and simple workup. Also, these novel magnetic nanocatalysts are superior to the industry standard Pd in every relevant aspect. They feature a way higher initial activity, a much more convenient separation, better recycling, and less contamination of the products. Last but not least, they can be very easily prepared from commercially available Fe3O4 nanoparticles using standard laboratory equipment.
Catalytic behavior tuning via structural modifications of silylated‐diphosphine Ni(II) complexes for ethylene selective dimerization
Authors: Wang Jiadong , Alam Fakhre , Chang Qiqi , Chen Yanhui , Jiang Tao
Published: May 2020

The methylene spacers and an uncoordinated diphenylphosphine moiety in the scaffold of the CH3Si(CH2)n(PPh2)3 and Si(CH2PPh2)4‐type silylated diphosphine Ni(II) complex systems have a marked impact on their catalytic performance in selective ethylene dimerization. Ni(II)‐based precatalyst 1, bearing two methylene spacers in its framework, exhibited the highest catalytic activity of 1.29 × 108 g (molNi)‐1 h‐1, while precatalyst 3, with three methylene spacers, affords the highest product selectivity (88%) toward the C4 fraction. Crystallographic investigations revealed that the precatalyst 3 adopts the mononuclear bidentate binding mode and the steric constraints of its uncoordinated diphenylphosphine moiety may successfully tailor the catalytic environment of the catalyst. The precatalyst 4 may form a dinuclear complex and exhibits high catalytic activity by changing the ligand/Ni molar ratio. The high C4 selectivity of precatalyst 3 has been rationalized by density functional theory (DFT) calculations and found to be consistent with the experimental results. The study also revealed that designing new systems of Ni(II)‐based complexes and their systematic modifications may further provide potential and industrially viable catalyst systems for selective ethylene oligomerization.
Too little but not too late? Biology of a recently discovered and imperilled freshwater fish in a drying temperate region and comparison with sympatric fishes
Authors: Allen Mark G. , Morgan David L. , Close Paul G. , Beatty Stephen J.
Published: May 2020

Small‐bodied freshwater fishes are commonly overlooked in threatened species management despite being highly imperilled. Before this study, the newly described little pygmy perch (Nannoperca pygmaea) was known from only 0.06 km2 of habitat in a single catchment in south‐western Australia and a lack of knowledge prevented an understanding of its conservation status and priority actions.

The present study determined the distribution, biology, and movement patterns of N. pygmaea and compared these with other small, sympatric percihthyids to assess its conservation status and likely resilience to threatening processes.

The current ‘extent of occurrence' of N. pygmaea was determined to be 3,420 km2 and the ‘area of occupancy' was 10 km2. Nannoperca pygmaea inhabited permanent refuge pools in the main stem of an ephemeral, secondarily salinized catchment where salinities remained <6 ppt during summer.

During winter N. pygmaea undertook a short upstream migration into a seasonally flowing freshwater tributary to serially spawn. The timing of reproduction was partitioned among three sympatric pygmy perches within the austral winter/spring period.

The species qualifies as ‘Endangered' under the IUCN Red List assessment criteria. Its restriction to freshwater refugia within salinized rivers suggests that N. pygmaea may have a limited salinity tolerance similar to the sympatric, threatened Nannatherina balstoni, and that the species is susceptible to prolonged drought, drying of critical baseflow refuges, increasing salinization, and introductions of alien species.

The study serves as an example that small‐bodied freshwater fishes need greater research attention to understand the biological and environmental mechanisms underpinning their decline.
Further evidence of superluminal active galactic nuclei as γ‐ray sources
Authors: Xiao Hubing , Fan Junhui , Rando Riccardo , Zhu Jingtian , Hu Liangjun
Published: May 2020

In our previous work in Xiao et al. (SCPMA, 2019, 62, 129811), we suggested that six superluminal sources could be γ‐ray candidates, and in fact, five of them have been confirmed in the fourth Fermi‐LAT source catalog (4FGL). In this work, based on the 4FGL, we report a sample of 229 Fermi detected superluminal sources (FDSs), including 40 new FDSs and 62 non‐FDSs. Thus, we believe that all superluminal sources should have γ‐ray emissions, and superluminal motion could also be a clue to detect γ‐ray emission from active galactic nuclei. We present a new approach of Doppler factor estimate through the study of the γ‐ray luminosity (Lγ) and of the viewing angle (ϕ).
A comparative analysis of raw and processed Radix Paeoniae Alba samples using HPLC, chemometrics, and antioxidant activity
Authors: You Guangjiao , Li Chenghao , Mao Yingying , Ren Xiaoliang , Liu Yanan , Wang Meng
Published: May 2020

Radix Paeoniae Alba (RPA) and its processed products are commonly used in traditional Chinese medicine, but the chaos phenomenon among processed products often occurs. In this study, we used multiple chemometric methods to analyze raw and six different processed products of RPA based on HPLC fingerprinting. Heat map analysis was used to assess the changes in chemical composition. Principal component analysis was used for classification, and the samples were divided into four classes: class 1 (raw, wine‐processed, and vinegar‐processed products), class 2 (bran‐processed and soil‐processed products), class 3 (stir‐fried products), and class 4 (coke products). Further, the orthogonal partial least squares discriminant analysis model was used to obtain chemical markers among different classes. The antioxidant property of RPA is an important factor responsible for its pharmacological effects, and so the antioxidant activity of RPA was also investigated. We measured 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH) and hydroxyl radical scavenging ability, and ferric reducing antioxidant power. The total antioxidant activity follows the order: coke > stir‐fried > soil‐processed > bran‐processed > wine‐processed > raw > vinegar‐processed products. These results suggest that different processing methods affect the chemical composition and antioxidant power of RPA, and thus, different products of RPA should not be mixed.
COVID‐19 complicated by acute myocardial infarction with extensive thrombus burden and cardiogenic shock
Authors: Harari Rafael , Bangalore Sripal , Chang Ernest , Shah Binita
Published: May 2020

A patient with coronavirus disease 19 (COVID‐19) developed acute myocardial infarction (AMI) complicated by extensive coronary thrombosis and cardiogenic shock. She underwent percutaneous coronary intervention and placement of a mechanical circulatory support device but subsequently died from shock. This report illustrates the challenges in managing patients with COVID‐19, AMI, and cardiogenic shock.
Industrial Crystallization: A Vital Process for the Modern Chemical Industry
Authors: Flood Adrian , Wantha Lek
Published: May 2020

No abstract.
Electronic Oxide–Metal Strong Interaction (EOMSI)
Authors: Qian Kun , Duan Huimei , Li Yangyang , Huang Weixin
Published: May 2020

Strong metal–support interaction of supported metal catalysts is an important concept to describe the effect of metal–support interactions on the structures and catalytic performances of supported metal particles. By using an example of CeOx adlayers supported on Ag nanocrystals, herein a concept of electronic oxide–metal strong interaction (EOMSI) is put forward; this interaction significantly affects the electronic structures of oxide adlayers through metal‐to‐oxide charge transfer. The EOMSI can stabilize oxide adlayers in a low oxidation state under ambient conditions, which individually are not stable; moreover, the oxide adlayers experiencing the EOMSI are resistant to high‐temperature oxidation in air to a certain extent. Such an EOMSI concept helps to generalize the strong influence of oxide–metal interactions on the structures and catalytic performance of oxide/metal inverse catalysts, which have been attracting increasing attention.
Phase Transition and Band Gap Regulation by Halogen Substituents on the Organic Cation in Organic–Inorganic Hybrid Perovskite Semiconductors
Authors: Cao Ying‐Jie , Zhou Lin , He Lei , Shi Ping‐Ping , Ye Qiong , Fu Da‐Wei
Published: May 2020

In the last decade, hybrid materials have received widespread attention. In particular, hybrid lead halide perovskite‐type semiconductors are very attractive owing to their great flexibility in band gap engineering. Here, by using precise molecular modifications, three one‐dimensional perovskite‐type semiconductor materials are designed and obtained: [Me3PCH2X][PbBr3] (X=H, F, and Cl for compounds 1, 2, and 3, respectively). The introduction of a heavier halogen atom (F or Cl) to [Me4P]+ increases the potential energy barrier required for the tumbling motion of the cation, hence achieving the transformation of the phase transition temperature from low temperature (192 K) to room temperature (285 K) and high temperature (402.3 K). Moreover, the optical band gaps reveal a broadening trend with 3.176 eV, 3.215 eV, and 3.376 eV along the H→F→Cl series, which is attributed to the formation of the structural distortion.
Self‐Assembly of Mitochondria‐Targeted Photosensitizer to Increase Photostability and Photodynamic Therapeutic Efficacy in Hypoxia
Authors: Jana Batakrishna , Thomas Ajesh P. , Kim Sangpil , Lee In Seong , Choi Huyeon , Jin Seongeon , Park Soo Ah , Min Seung Kyu , Kim Chaekyu , Ryu Ja‐Hyoung
Published: May 2020

The development of photosensitizers for cancer photodynamic therapy has been challenging due to their low photostability and therapeutic inefficacy in hypoxic tumor microenvironments. To overcome these issues, we have developed a mitochondria‐targeted photosensitizer consisting of an indocyanine moiety with triphenylphosphonium arms, which can self‐assemble into spherical micelles directed to mitochondria. Self‐assembly of the photosensitizer resulted in a higher photostability by preventing free rotation of the indoline ring of the indocyanine moiety. The mitochondria targeting capability of the photosensitizer allowed it to utilize intramitochondrial oxygen. We found that the mitochondria‐targeted photosensitizer localized to mitochondria and induced apoptosis of cancer cells both normoxic and hypoxic conditions through generation of ROS. The micellar self‐assemblies of the photosensitizer were further confirmed to selectively localize to tumor tissues in a xenograft tumor mouse model through passive targeting and showed efficient tumor growth inhibition.
London Dispersion and Hydrogen‐Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes
Authors: Quesada Moreno María Mar , Pinacho Pablo , Pérez Cristóbal , Šekutor Marina , Schreiner Peter R. , Schnell Melanie
Published: May 2020

Diadamantyl ether (DAE, C20H30O) represents a good model to study the interplay between London dispersion and hydrogen‐bond interactions. By using broadband rotational spectroscopy, an accurate experimental structure of the diadamantyl ether monomer is obtained and its aggregates with water and a variety of aliphatic alcohols of increasing size are analyzed. In the monomer, C−H⋅⋅⋅H−C London dispersion attractions between the two adamantyl subunits further stabilize its structure. Water and the alcohol partners bind to diadamantyl ether through hydrogen bonding and non‐covalent Owater/alcohol⋅⋅⋅H−CDAE and C−Halcohol⋅⋅⋅H−CDAE interactions. Electrostatic contributions drive the stabilization of all the complexes, whereas London dispersion interactions become more pronounced with increasing size of the alcohol. Complexes with dominant dispersion contributions are significantly higher in energy and were not observed in the experiment. The results presented herein shed light on the first steps of microsolvation and aggregation of molecular complexes with London dispersion energy donor (DED) groups and the kind of interactions that control them.
Tetrahydroimidazo[1,2‐a]pyrazine Derivatives: Synthesis and Evaluation as Gαq‐Protein Ligands
Authors: Küppers Jim , Benkel Tobias , Annala Suvi , Kimura Kenichi , Reinelt Lisa , Fleischmann Bernd K. , Kostenis Evi , Gütschow Michael
Published: May 2020

The 5,6,7,8‐tetrahydroimidazo[1,2‐a]pyrazine derivative BIM‐46174 and its dimeric form BIM‐46187 (1) are heterocyclized dipeptides that belong to the very few cell‐permeable compounds known to preferentially silence Gαq proteins. To explore the chemical space of Gαq inhibitors of the BIM chemotype, a combinatorial approach was conducted towards a library of BIM molecules. This library was evaluated in a second messenger‐based fluorescence assay to analyze the activity of Gαq proteins through the determination of intracellular myo‐inositol 1‐phosphate. Structure–activity relationships were deduced and structural requirements for biological activity obtained, which were (i) a redox reactive thiol/disulfane substructure, (ii) an N‐terminal basic amino group, (iii) a cyclohexylalanine moiety, and (iv) a bicyclic skeleton. Active compounds exhibited cellular toxicity, which was investigated in detail for the prototypical inhibitor 1. This compound affects the structural cytoskeletal dynamics in a Gαq/11‐independent manner.
Resonance Assisted Hydrogen Bonding Phenomenon Unveiled through Both Experiments and Theory: A New Family of Ethyl N‐Salicylideneglycinate Dyes
Authors: Shapenova Dinara S. , Shiryaev Alexey A. , Bolte Michael , Kukułka Mercedes , Szczepanik Dariusz W. , Hooper James , Babashkina Maria G. , Mahmoudi Ghodrat , Mitoraj Mariusz P. , Safin Damir A.
Published: May 2020

Extensive experimental and theoretical investigations are reported on the nature of resonance‐assisted hydrogen bonding phenomenon (RAHB) and its influence on photophysical properties of the newly designed dyes differing in donor–acceptor properties, namely ethyl N‐salicylideneglycinate (1), ethyl N‐(5‐methoxysalicylidene)glycinate (2), ethyl N‐(5‐bromosalicylidene)glycinate (3) and ethyl N‐(5‐nitrosalicylidene)glycinate (4). All compounds are thermochromic in the solid state and they contain a typical intramolecular O−H⋅⋅⋅N hydrogen bond formed between the hydroxyl hydrogen atom and the imine nitrogen atom, yielding the enol form in the solid state. It is unveiled, that the magnitude of RAHB effect fine tunes the strength of the O−H⋅⋅⋅N bonding and accordingly the relative populations of the enol, cis‐keto and trans‐keto forms leading to variation of the photophysical properties of 1–4. It is determined, that the electron‐withdrawing NO2 in 4 amplifies the most RAHB effect causing the breaking of the O−H⋅⋅⋅N hydrogen bond and accordingly formation of the dominant cis‐keto isomer in both the solid state and EtOH. To this end, the UV/Vis spectra of 1–3 in EtOH revealed the exclusive presence of the enol form, while the prevalent contribution of the cis‐keto form was found for 4. Furthermore, only compound 4 is emissive in the solid state in ambient condition due to dual emission arising from the cis‐keto* and trans‐keto* forms, while 2 was found to be highly emissive in EtOH. It is revealed qualitatively and quantitatively, based on the ETS‐NOCV charge and energy decomposition scheme and the EDDB population‐based method, that RAHB is strongly a non‐local phenomenon based on electrons pumping or sucking through both the π‐ and σ‐channels, which accordingly exerts chemical bonding changes at both the phenyl ring and predominantly a distant O−H⋅⋅⋅N area.
An Air‐ and Water‐Stable Hydrogen‐Bond‐Donor Catalyst for the Enantioselective Generation of Quaternary Carbon Stereocenters by Additions of Substituted Cyanoacetate Esters to Acetylenic Esters
Authors: Luu Quang H. , Gladysz John A.
Published: May 2020

The chiral enantiopure cobalt(III) complex Δ‐[Co((S,S)‐dpen)3]3+ 2Cl−B(C6F5)4− (Δ‐(S,S)‐23+ 2Cl−B(C6F5)4−; dpen=1,2‐diphenylethylenediamine) is an effective catalyst, together with pyridine (10 mol % each), for enantioselective additions of substituted cyanoacetate esters NCCH(R)CO2R′ to acetylenic esters R′′C≡CCO2R′′′. In the resulting adducts NC(R′O2C)C(R)CR′′C=CHCO2R′′′, C=C isomers in which the CO2R′′′ moiety is trans to the new carbon–carbon bond dominate (avg. ratio 98:2). These are obtained in 70–98 % ee (avg. 86 %; data for optimum R′ and R′′′), as determined by 1H NMR with the chiral solvating agent Λ‐(S,S)‐23+ 2I−B(3,5‐C6H3(CF3)2)4−. NMR experiments show that the cyanoacetate and acetylenic esters and pyridine can hydrogen bond to certain NH groups of the catalyst. Rates are zero order in the cyanoacetate and acetylenic esters as well as the catalyst, and implications are discussed.
Hydrogen‐Bond Catalysis of Imine Exchange in Dynamic Covalent Systems
Authors: Schaufelberger Fredrik , Seigel Karolina , Ramström Olof
Published: May 2020

The reversibility of imine bonds has been exploited to great effect in the field of dynamic covalent chemistry, with applications such as preparation of functional systems, dynamic materials, molecular machines, and covalent organic frameworks. However, acid catalysis is commonly needed for efficient equilibration of imine mixtures. Herein, it is demonstrated that hydrogen bond donors such as thioureas and squaramides can catalyze the equilibration of dynamic imine systems under unprecedentedly mild conditions. Catalysis occurs in a range of solvents and in the presence of many sensitive additives, showing moderate to good rate accelerations for both imine metathesis and transimination with amines, hydrazines, and hydroxylamines. Furthermore, the catalyst proved simple to immobilize, introducing both reusability and extended control of the equilibration process.
Modeling the Reaction of Carboxylic Acids and Isonitriles in a Self‐Assembled Capsule
Authors: Daver Henrik , Rebek Julius , Himo Fahmi
Published: May 2020

Quantum chemical calculations were used to study the reaction of carboxylic acids with isonitriles inside a resorcinarene‐based self‐assembled capsule. Experimentally, it has been shown that the reactions between p‐tolylacetic acid and n‐butyl isonitrile or isopropyl isonitrile behave differently in the presence of the capsule compared both with each other and also with their solution counterparts. Herein, the reasons for these divergent behaviors are addressed by comparing the detailed energy profiles for the reactions of the two isonitriles inside and outside the capsule. An energy decomposition analysis was conducted to quantify the different factors affecting the reactivity. The calculations reproduce the experimental findings very well. Thus, encapsulation leads to lowering of the energy barrier for the first step of the reaction, the concerted α‐addition and proton transfer, which in solution is rate‐determining, and this explains the rate acceleration observed in the presence of the capsule. The barrier for the final step of the reaction, the 1,3 O→N acyl transfer, is calculated to be higher with the isopropyl substituent inside the capsule compared with n‐butyl. With the isopropyl substituent, the transition state and the product of this step are significantly shorter than the preceding intermediate, and this results in energetically unfavorable empty spaces inside the capsule, which cause a higher barrier. With the n‐butyl substituent, on the other hand, the carbon chain can untwine and hence uphold an appropriate guest length.
Electrophilic Chlorine from Chlorosulfonium Salts: A Highly Chemoselective Reduction of Sulfoxides
Authors: Acosta‐Guzmán Paola , Mahecha‐Mahecha Camilo , Gamba‐Sánchez Diego
Published: May 2020

Herein, we describe a selective late‐stage deoxygenation of sulfoxides based on a novel application of chlorosulfonium salts and demonstrate a new process using these species generated in situ from sulfoxides as the source of electrophilic chlorine. The use of highly nucleophilic 1,3,5‐trimethoxybenzene (TMB) as the reducing agent is described for the first time and applied in the deoxygenation of simple and functionalized sulfoxides. The method is easy to handle, economic, suitable for gram‐scale operations, and readily applied for poly‐functionalized molecules, as demonstrated with more than 45 examples, including commercial medicines and analogues. We also report the results of competition experiments that define the more reactive sulfoxide and we present a mechanistic proposal based on substrate and product observations.
Synthesis of Nitro‐Aryl Functionalised 4‐Amino‐1,8‐Naphthalimides and Their Evaluation as Fluorescent Hypoxia Sensors
Authors: Adair Liam D. , Trinh Natalie , Vérité Pauline M. , Jacquemin Denis , Jolliffe Katrina A. , New Elizabeth J.
Published: May 2020

Fluorescent sensors are a vital research tool, enabling the study of intricate cellular processes in a sensitive manner. The design and synthesis of responsive and targeted probes is necessary to allow such processes to be interrogated in the cellular environment. This remains a challenge, and requires methods for functionalisation of fluorophores with multiple appendages for sensing and targeting groups. Methods to synthesise more structurally complex derivatives of fluorophores will expand their potential scope. Most known 4‐amino‐1,8‐naphthalimides are only functionalised at imide and 4‐positions, and structural modifications at additional positions will increase the breadth of their utility as responsive sensors. In this work, methods for the incorporation of a hypoxia sensing group to 4‐amino‐1,8‐naphthalimide were evaluated. An intermediate was developed that allowed us to incorporate a sensing group, targeting group, and ICT donor to the naphthalimide core in a modular fashion. Synthetic strategies for attaching the hypoxia sensing group and how they affected the fluorescence of the naphthalimide were evaluated by photophysical characterisation and time‐dependent density functional theory. An extracellular hypoxia probe was then rationally designed that could selectively image the hypoxic and necrotic region of tumour spheroids. Our results demonstrate the versatility of the naphthalimide scaffold and expand its utility. This approach to probe design will enable the flexible, efficient generation of selective, targeted fluorescent sensors for various biological purposes.
Co Single‐Atom Catalysts Boost Chemiluminescence
Authors: Ouyang Hui , Zhang Lvxia , Jiang Shan , Wang Wenwen , Zhu Chengzhou , Fu Zhifeng
Published: May 2020

Co single‐atom catalysts (SACs) with good aqueous solubility and abundant labelling functional groups were prepared in Co/Fe bimetallic metal‐organic frameworks by a facile solvothermal method without high‐temperature calcination. In contrast to traditional chemiluminescence (CL) catalysts, Co SACs accelerated decomposition of H2O2 to produce a large amount of singlet oxygen (1O2) rather than superoxide (O2.−) and hydroxyl radical (OH.). They were found to dramatically enhance the CL emission of the luminol‐H2O2 reaction by 1349 times, and, therefore, were employed as very sensitive signal probes for conducting CL immunoassay of cardiac troponin I. The detection limit of the target analyte was as low as 3.3 pg mL−1. It is the first time that employment of SACs for boosting CL reactions has been validated. The Co SACs can also be employed to trace other biorecognition events with high sensitivity.
Photoredox‐Catalyzed Addition of Carbamoyl Radicals to Olefins: A 1,4‐Dihydropyridine Approach
Authors: Cardinale Luana , Konev Mikhail O. , Jacobi von Wangelin Axel
Published: May 2020

Functionalization with C1‐building blocks are key synthetic methods in organic synthesis. The low reactivity of the most abundant C1‐molecule, carbon dioxide, makes alternative carboxylation reactions with CO2‐surrogates especially important. We report a photoredox‐catalyzed protocol for alkene carbamoylations. Readily accessible 4‐carboxamido‐Hantzsch esters serve as convenient starting materials that generate carbamoyl radicals upon visible light‐mediated single‐electron transfer. Addition to various alkenes proceeded with high levels of regio‐ and chemoselectivity.
A Review on Particle Size Effect in Metal‐Catalyzed Heterogeneous Reactions
Authors: Wang Hengwei , Lu Junling
Published: May 2020

Size of metal nanoparticles (NPs) plays decisive roles in metal‐catalyzed heterogeneous reactions, due to the drastic variation of the geometric and electronic properties of metal NPs with size. Along with the development of controlled catalyst synthesis, tremendous efforts have been devoted to understanding the nature of the particle size effect. In particular, identification of the individual roles of size‐dependent geometric and electronic effects on metal‐catalyzed reactions is essential, but remains challenging since they are tightly hybridized together with particle size variation. In this review, we first discuss the fundamentals of the size‐dependent geometric and electronic properties of metal NPs and their crucial roles in catalysis in general. Then we summarize the previous representative studies of the particle size effect, metal‐by‐metal, in heterogeneous catalysis. We highlighted the extension of particle size effect to ultrafine cluster and single‐atom catalysts, the new frontiers in heterogeneous catalysis. In the followings, we further introduce the recent advances in disentangling the size‐dependent geometric and electronic effects and unveiling their individual contributions to catalysis. Finally, we discuss the challenges and perspectives of investigations on the size effect in metal catalysis for the future studies.
Impact of diabetes mellitus and hemoglobin A1c level on outcomes among Chinese patients with acute coronary syndrome
Authors: Xiong Ran , He Liu , Du Xin , Dong Jian‐Zeng , Ma Chang‐Sheng
Published: May 2020

Background

The impact of different glycemic control conditions on in‐hospital and long‐term outcomes among patients with acute coronary syndrome (ACS) is less well defined.

Hypothesis

Diabetes mellitus (DM) with different admission hemoglobin A1c (HbA1c) levels (different glycemic control) could affect outcomes among Chinese patients hospitalized as ACS.

Methods

We categorized 8961 Chinese ACS patients into one of the following three groups: “no DM” (group 1, n = 3773; no DM history and admission HbA1c < 6.5%), “DM with optimal control”(group 2, n = 2241; DM with admission HbA1c < 7.0%), “DM with suboptimal control”(group 3, n = 2947; DM with admission HbA1c ≥ 7.0%). The primary outcome was in‐hospital major adverse cardiovascular events (MACEs). 6098 patients were followed for a median of 3.85 years. Adjusted associations of these three groups with in‐hospital MACEs and long‐term mortality were determined.

Results

DM with suboptimal control (group 3) was associated with greater in‐hospital MACEs (OR 1.46, 95% CI 1.17‐1.81, P = .001) than “no DM” (group 1). DM patients (group 2 and group 3) also had higher in‐hospital MACEs (OR 1.42, 95% CI 1.16‐1.73, P = .001) than “no DM” patients (group 1). It showed no significantly different in‐hospital MACEs between optimal (group 2) and suboptimal (group 3) control group (OR 1.06, 95% CI 0.84‐1.34, P = .63). Both optimal control (group 2) and suboptimal control (group 3) had a higher long‐term mortality (HR 1.26, 95% CI 1.02‐1.56, P = .03; HR 1.42, 95% CI 1.16‐1.73, P = .001).

Conclusions

ACS patients with DM were associated with higher in‐hospital MACEs and long‐term mortality. Moreover, lower HbA1c level seems to have limited impact on cardiovascular events and long‐term mortality in this high‐risk population.
Second cancer risk after primary cancer treatment with three‐dimensional conformal, intensity‐modulated, or proton beam radiation therapy
Authors: Xiang Michael , Chang Daniel T. , Pollom Erqi L.
Published: May 2020

Background

The comparative risks of a second cancer diagnosis are uncertain after primary cancer treatment with 3‐dimensional conformal radiotherapy (3DCRT), intensity‐modulated radiotherapy (IMRT), or proton beam radiotherapy (PBRT).

Methods

Pediatric and adult patients with a first cancer diagnosis between 2004 and 2015 who received 3DCRT, IMRT, or PBRT were identified in the National Cancer Database from 9 tumor types: head and neck, gastrointestinal, gynecologic, lymphoma, lung, prostate, breast, bone/soft tissue, and brain/central nervous system. The diagnosis of second cancer was modeled using multivariable logistic regression adjusting for age, follow‐up duration, radiotherapy (RT) dose, chemotherapy, sociodemographic variables, and other factors. Propensity score matching also was used to balance baseline characteristics.

Results

In total, 450,373 patients were identified (33.5% received 3DCRT, 65.2% received IMRT, and 1.3% received PBRT) with median follow‐up of 5.1 years after RT completion and a cumulative follow‐up period of 2.54 million person‐years. Overall, the incidence of second cancer diagnosis was 1.55 per 100 patient‐years. In a comparison between IMRT versus 3DCRT, there was no overall difference in the risk of second cancer (adjusted odds ratio [OR], 1.00; 95% CI, 0.97‐1.02;P = .75). By comparison, PBRT had an overall lower risk of second cancer versus IMRT (adjusted OR, 0.31; 95% CI, 0.26‐0.36;P < .0001). Results within each tumor type generally were consistent in the pooled analyses and also were maintained in propensity score‐matched analyses.

Conclusions

The risk of a second cancer diagnosis was similar after IMRT versus 3DCRT, whereas PBRT was associated with a lower risk of second cancer risk. Future work is warranted to determine the cost‐effectiveness of PBRT and to identify the population best suited for this treatment.
Importance of quality‐of‐life priorities and preferences surrounding treatment decision making in patients with cancer and oncology clinicians
Authors: Williams Courtney P. , Miller‐Sonet Ellen , Nipp Ryan D. , Kamal Arif H. , Love Susan , Rocque Gabrielle B.
Published: May 2020

Background

Shared decision‐making (SDM) occurs when a patient partners with their oncologist to integrate personal preferences and values into treatment decisions. A key component of SDM is the elicitation of patient preferences and values, yet little is known about how and when these are elicited, communicated, prioritized, and documented within clinical encounters.

Methods

This cross‐sectional study evaluated nationwide data collected by CancerCare to better understand current patterns of SDM between patients and their oncology clinicians. Patient surveys included questions about the importance of quality‐of‐life preferences and discussions regarding quality‐of‐life priorities with their clinicians. Clinician surveys included questions about the discussion of quality‐of‐life priorities and preferences with patients, the effect of quality‐of‐life priorities on treatment recommendations, and quality‐of‐life priority documentation in practice.

Results

Patient survey completers (n = 320; 33% response rate) were predominantly women (95%), had a diagnosis of breast cancer (59%), or were receiving active cancer treatment (59%). Clinician survey completers (n = 112; 5% response rate) predominately identified as hematologists or oncologists (66%). Although 67% of clinicians reported knowing their patients' personal quality‐of‐life priorities and preferences before finalizing treatment plans, only 37% of patients reported that these discussions occurred before treatment initiation. Most patients (95%) considered out‐of‐pocket expenses important during treatment planning, yet only 59% reported discussing out‐of‐pocket expenses with their clinician before finalizing treatment plans. A majority of clinicians (52%) considered clinic questionnaires as feasible to document quality‐of‐life priorities and preferences.

Conclusions

Patients and clinicians reported that preferences related to quality‐of‐life should be considered in treatment decision making, yet barriers to SDM, preference elicitation, and documentation remain.
Fabrication of Template‐Less Self‐Propelled Micromotors Based on A Metal‐Sandwiched Polytryptophan Body: An Experimental and DFT Study
Authors: Moradi Nozar , Shamsipur Mojtaba , Taherpour Avat (Arman) , Rahimdad Nastaran , Pashabadi Afshin
Published: May 2020

The diverse capabilities of self‐propelled micro/nanomotors open up significant opportunities for various environmental and biomedical applications. Here, a synchronized two‐lobed bubble exhaust drives micromotor comprising a metal (cobalt and gold) sandwiched polytryptophan body (Au/poly‐Trp/Co) in a non‐curved direction. The autonomous motion is achieved through the decomposition of chemical fuel to result in a kayak‐like system. The ejected oxygen bubbles from the interfacial cobalt/polytryptophan layer, as well as the inert nature of the metal segments (Au−Co), were considered for some computational studies of the electronic properties of the composite and physical phenomena at the kayak/electrolyte interfaces, and confirmed the role of Co−Trp in the fuel decomposition. It is believed that the autonomous motion is the combined result of bubble recoil force, self‐electrophoresis, and perturbation in the interfacial hydrogen‐bond network of the poly‐Trp body and water molecules. The velocity of the micromotor in the range 23±4 to 157±17 μm s−1 at different concentrations of H2O2 from 1 % to 10 %. Depending on the method of fragmentation, it is possible to have both single and multiple motorized kayaks with lengths of 1.5 and 6 μm, respectively, that can be tailored for environmental applications.
Provide leadership to address economic impact of pandemic
Authors: Hope Joan
Published: May 2020

“What should I be doing when I really don't know what will happen next? What can I learn?” Those are questions higher education leaders should be asking over the next few months about the impacts of the COVID‐19 pandemic, said Larenda Mielke, Vice President of Higher Education at Kaufman Hall.
Abundance, origin, and phylogeny of plants do not predict community‐level patterns of pathogen diversity and infection
Authors: Schmidt Robin , Auge Harald , Deising Holger B. , Hensen Isabell , Mangan Scott A. , Schädler Martin , Stein Claudia , Knight Tiffany M.
Published: May 2020

Pathogens have the potential to shape plant community structure, and thus, it is important to understand the factors that determine pathogen diversity and infection in communities. The abundance, origin, and evolutionary relationships of plant hosts are all known to influence pathogen patterns and are typically studied separately. We present an observational study that examined the influence of all three factors and their interactions on the diversity of and infection of several broad taxonomic groups of foliar, floral, and stem pathogens across three sites in a temperate grassland in the central United States. Despite that pathogens are known to respond positively to increases in their host abundances in other systems, we found no relationship between host abundance and either pathogen diversity or infection. Native and exotic plants did not differ in their infection levels, but exotic plants hosted a more generalist pathogen community compared to native plants. There was no phylogenetic signal across plants in pathogen diversity or infection. The lack of evidence for a role of abundance, origin, and evolutionary relationships in shaping patterns of pathogens in our study might be explained by the high generalization and global distributions of our focal pathogen community, as well as the high diversity of our plant host community. In general, the community‐level patterns of aboveground pathogen infections have received less attention than belowground pathogens, and our results suggest that their patterns might not be explained by the same drivers.
Diversification in evolutionary arenas—Assessment and synthesis
Authors: Nürk Nicolai M. , Linder H. Peter , Onstein Renske E. , Larcombe Matthew J. , Hughes Colin E. , Piñeiro Fernández Laura , Schlüter Philipp M. , Valente Luis , Beierkuhnlein Carl , Cutts Vanessa , Donoghue Michael J. , Edwards Erika J. , Field Richard , Flantua Suzette G. A. , Higgins Steven I. , Jentsch Anke , Liede‐Schumann Sigrid , Pirie Michael D.
Published: May 2020

Understanding how and why rates of evolutionary diversification vary is a key issue in evolutionary biology, ecology, and biogeography. Evolutionary rates are the net result of interacting processes summarized under concepts such as adaptive radiation and evolutionary stasis. Here, we review the central concepts in the evolutionary diversification literature and synthesize these into a simple, general framework for studying rates of diversification and quantifying their underlying dynamics, which can be applied across clades and regions, and across spatial and temporal scales. Our framework describes the diversification rate (d) as a function of the abiotic environment (a), the biotic environment (b), and clade‐specific phenotypes or traits (c); thus,d ~ a,b,c. We refer to the four components (a–d) and their interactions collectively as the “Evolutionary Arena.” We outline analytical approaches to this framework and present a case study on conifers, for which we parameterize the general model. We also discuss three conceptual examples: theLupinusradiation in the Andes in the context of emerging ecological opportunity and fluctuating connectivity due to climatic oscillations; oceanic island radiations in the context of island formation and erosion; and biotically driven radiations of the Mediterranean orchid genusOphrys. The results of the conifer case study are consistent with the long‐standing scenario that low competition and high rates of niche evolution promote diversification. The conceptual examples illustrate how using the synthetic Evolutionary Arena framework helps to identify and structure future directions for research on evolutionary radiations. In this way, the Evolutionary Arena framework promotes a more general understanding of variation in evolutionary rates by making quantitative results comparable between case studies, thereby allowing new syntheses of evolutionary and ecological processes to emerge.
Myeloperoxidase and related biomarkers are suggestive footprints of endothelial microvascular inflammation in HFpEF patients
Authors: Hage Camilla , Michaëlsson Erik , Kull Bengt , Miliotis Tasso , Svedlund Sara , Linde Cecilia , Donal Erwan , Daubert Jean‐Claude , Gan Li‐Ming , Lund Lars H.
Published: May 2020

Aims

In heart failure (HF) with preserved ejection fraction (HFpEF), microvascular inflammation is proposed as an underlying mechanism. Myeloperoxidase (MPO) is associated with vascular dysfunction and prognosis in congestive HF.

Methods and results

MPO, MPO‐related biomarkers, and echocardiography were assessed in 86 patients, 4–8 weeks after presentation with acute HF (EF ≥ 45%), and in 46 healthy controls. Patients were followed up for median 579 days (Q1;Q3 276;1178) regarding the composite endpoint all‐cause mortality or HF hospitalization. Patients were 73 years old, 51% were female, EF was 64% (Q1;Q3 58;68), E/e′ was ratio 10.8 (8.3;14.0), and left atrial volume index (LAVI) was 43 mL/m2 (38;52). Controls were 60 (57;62) years old (vs. patients; P < 0.001), 24% were female (P = 0.005), and left ventricular EF was 63% (59;66; P = 0.790). MPO was increased in HFpEF compared with controls, 101 (81;132) vs. 86 (74;101 ng/mL, P = 0.015), as was uric acid 369 (314;439) vs. 289 (252;328 μmol/L, P < 0.001), calprotectin, asymmetric dimethyl arginine (ADMA), and symmetric dimethyl arginine (SDMA), while arginine was decreased. MPO correlated with uric acid (r = 0.26; P = 0.016). In patients with E/e′ > 14, uric acid and SDMA were elevated (421 vs. 344 μM, P = 0.012; 0.54 vs. 0.47 μM, P = 0.039, respectively), and MPO was 121 vs. 98 ng/mL (P = 0.090). The ratios of arginine/ADMA (112 vs. 162; P < 0.001) and ADMA/SDMA (1.36 vs. 1.17; P = 0.002) were decreased in HFpEF patients, suggesting reduced NO availability and increased enzymatic clearance of ADMA, respectively. Uric acid independently predicted the endpoint [hazard ratio (HR) 3.76 (95% CI 1.19–11.85; P = 0.024)] but not MPO [HR 1.48 (95% CI 0.70–3.14; P = 0.304)] or the other biomarkers.

Conclusions

In HFpEF, MPO‐dependent oxidative stress reflected by uric acid and calprotectin is increased, and SDMA is associated with diastolic dysfunction and uric acid with outcome. This suggests microvascular neutrophil involvement mirroring endothelial dysfunction, a central component of the HFpEF syndrome and a potential treatment target.
Thermal transport analysis for natural convection in a porous corrugated rhombic enclosure
Authors: Dutta Shantanu , Pati Sukumar , Biswas Arup Kumar
Published: May 2020

A numerical study of fluid flow and heat transfer, applying natural convection is carried out in a porous corrugated rhombic enclosure. A uniform heating source is applied from the bottom boundary wall while the inclined side walls are maintained to a constant cold temperature and the top corrugated wall is retained at insulated condition inside the enclosure. The heat transfer and flow features are presented for a wide spectrum of Rayleigh numbers (Ra), 104 ≤ Ra ≤ 106, and Darcy numbers (Da), 10−3 ≤ Da ≤ 10−2. The number of undulations (n) for the top and bottom walls have been varied from 1 to 13 keeping the amplitude of undulation fixed. It is revealed that the characteristics of heat transfer are conceivably modulated by changing the parameter of the undulation number on the enclosure walls, specifically at the bottom and top. The influencing control of n in altering the heat transfer rate is felt maximum on the left wall and minimum for the right wall, and there is a strong interplay between Ra and Da together with n on dictating the heat transfer characteristics. The critical value, where heat transfer rate is observed as maximum is at n = 11 and thereafter the values decrease.
Oxaliplatin‐induced neuropathic pain involves HOXA6 via a TET1‐dependent demethylation of the SOX10 promoter
Authors: Deng Jie , Ding Huan‐Huan , Long Jia‐Li , Lin Su‐Yan , Liu Meng , Zhang Xue‐Qin , Xin Wen‐Jun , Ruan Xiangcai
Published: May 2020

Chemotherapy‐induced neuropathic pain is a common dose‐limiting side effect of cancer treatment but the underlying mechanisms are largely unknown. Here, we used a whole‐genome expression microarray and gene ontology analysis to identify the upregulation of a sequence‐specific DNA‐binding protein, HOXA6, in the spinal dorsal horn on Day 10 after injection of rats with oxaliplatin. Genetic disruption of HOXA6 with siRNAs alleviated mechanical allodynia after oxaliplatin administration. Reduced representation bisulfite sequencing assays indicated that oxaliplatin decreased the methylation levels of the SOX10 promoter but not of HOXA6. TET1 was also upregulated by oxaliplatin. Genetic disruption of TET1 with siRNA blocked the promoter demethylation of SOX10 and the upregulation of HOXA6 and SOX10. Importantly, inhibition of SOX10 by intrathecal application of SOX10 siRNA ameliorated the mechanical allodynia induced by oxaliplatin and downregulated the expression of HOXA6. Consistently, overexpression of SOX10 through intraspinal injection of AAV‐SOX10‐EGFP produced mechanical allodynia and upregulated the expression of spinal dorsal horn HOXA6. Moreover, chromatin immunoprecipitation assays demonstrated that oxaliplatin increased the binding of SOX10 to the promoter region of HOXA6. Taken together, our data suggest that HOXA6 upregulation through the TET1‐mediated promoter demethylation of SOX10 may contribute to oxaliplatin‐induced neuropathic pain.
Parallel astrocyte calcium signaling modulates olfactory bulb responses
Authors: Ung Kevin , Tepe Burak , Pekarek Brandon , Arenkiel Benjamin R. , Deneen Benjamin
Published: May 2020

Astrocytes are the most abundant glial cell in the central nervous system. They modulate synaptic function through a variety of mechanisms, and yet remain relatively understudied with respect to overall neuronal circuit function. Exploiting the tractability of the mouse olfactory system, we manipulated astrocyte activity and examined how astrocytes modulate olfactory bulb responses. Toward this, we genetically targeted both astrocytes and neurons for in vivo widefield imaging of Ca2+ responses to odor stimuli. We found that astrocytes exhibited odor response maps that overlap with excitatory neuronal activity. By manipulating Ca2+ activity in astrocytes using chemical genetics we found that odor‐evoked neuronal activity was reciprocally affected, suggesting that astrocyte activation inhibits neuronal odor responses. Subsequently, behavioral experiments revealed that astrocyte manipulations affect both odor detection threshold and discrimination, suggesting that astrocytes play an active role in olfactory sensory processing circuits. Together, these studies show that astrocyte calcium signaling contributes to olfactory behavior through modulation of sensory circuits.
Three Modes of Creativity
Authors: Creely Edwin , Henriksen Danah , Henderson Michael
Published: May 2020

This article is an ontological investigation of the term creativity, to suggest a model that infuses key philosophical and critical perspectives. This article proposes that creativity has three modes of existence or ways of being in the world: the Visceral (embodiments), the Ideational (mind and conceptual), and the Observational (appreciation, critical, and evaluative). We view creativity synergistically as representing both the individual creative experience and output, in conceptual and embodied ways—and also what externally shapes, enhances, and constrains creative experience. Technologies, as tools to think or create with, often mediate the operation of these three modes. We discuss each mode, instantiating it in an educational exemplar, and also engage with issues of power, discourse, and gatekeeping over what is deemed to be creative in education. Our discussion examines the rhetoric around the term, as well as issues of access to technologies that afford creativity. This tri‐modal model of creativity offers an interdisciplinary framework to complement existing models for understanding creativity.