bluuebunny/crossref_metadata_2025 huggingface dataset:
Fano‐Like Acoustic Resonance for Subwavelength Directional Sensing: 0–360 Degree Measurement
Authors: Lee Taehwa , Nomura Tsuyoshi , Su Xiaoshi , Iizuka Hideo
Published: January 2020

Directional sound sensing plays a critical role in many applications involving the localization of a sound source. However, the sensing range limit and fabrication difficulties of current acoustic sensing technologies pose challenges in realizing compact subwavelength direction sensors. Here, a subwavelength directional sensor is demonstrated, which can detect the angle of an incident wave in a full angle range (0°∼360°). The directional sensing is realized with acoustic coupling of Helmholtz resonators each supporting a monopolar resonance, which are monitored by conventional microphones. When these resonators scatter sound into free‐space acoustic modes, the scattered waves from each resonator interfere, resulting in a Fano‐like resonance where the spectral responses of the constituent resonators are drastically different from each other. This work provides a critical understanding of resonant coupling as well as a viable solution for directional sensing.
Graded Bandgap Perovskite with Intrinsic n–p Homojunction Expands Photon Harvesting Range and Enables All Transport Layer‐Free Perovskite Solar Cells
Authors: Sun Haoxuan , Deng Kaimo , Xiong Jie , Li Liang
Published: January 2020

Organic–inorganic halide perovskites are promising materials for next‐generation photovoltaic device due to their attractive photoelectrical properties such as strong light absorption, high carrier mobility, and tunable bandgap. Generally, perovskite solar cells require carrier transport layers (CTL) to provide a built‐in electric field and reduce the recombination rate. However, the construction of suitable electron‐ and hole‐transport layers is not cost effective, impairing the commercial application of the devices. An n–p perovskite homojunction absorber with a graded bandgap is developed by introducing a three‐step dynamic spin‐coating strategy and variable valence Sn elements. The bandgap of the perovskite absorber is gradually manipulated from 1.53 eV (the bottom) to 1.27 eV (the top). The electronic behavior is also transformed from n‐type (excess PbI2, the bottom) to p‐type (Sn vacancy, the top) in a very short distance (50 nm). This designed perovskite homojunction electronic structure not only expands the light harvesting range from 800 to 970 nm which provides potential to break the PCE limits, but also promotes oriented carrier transportation and weakens the dependence on CTL. The demonstrated asymmetrical active layer shows a brand‐new approach to simplify the device structure and boost the performance of CTL‐free perovskite solar cells.
Übergangsmetallvermittelte Spaltung von C‐C‐Einfachbindungen
Authors: Wang Brian , Perea Melecio A. , Sarpong Richmond
Published: January 2020

Eine übergangsmetallvermittelte Spaltung von C‐C‐Einfachbindungen kann eine völlig neue Retrosynthesestrategie in der Naturstoffsynthese ermöglichen. Da eine C‐C‐Bindungsspaltung das Kohlenstoffgerüst einer Verbindung stets ändert und das unter Übergangsmetallkatalyse erzeugte metallorganische oder radikalische Intermediat für den Aufbau größerer Komplexität geeignet ist, eröffnen sich durch diese C‐C‐Bindungsspaltungen neue Möglichkeiten zum drastischen und schnellen Umbau von Gerüstsystemen. Die jüngste Zunahme bei der Zahl der Anwendungen übergangsmetallvermittelter Spaltungen von C‐C‐Einfachbindungen in der Totalsynthese kann auf die allgemeine Anerkennung dieser Tatsache zurückgeführt werden. In diesem Aufsatz werden zehn Totalsynthesen von 2014 bis 2019 beleuchtet, in denen gezeigt wird, wie die übergangsmetallvermittelte C‐C‐Einfachbindungsspaltung am Kern oder an der Peripherie synthetischer Intermediate die Synthesebemühungen beschleunigen kann.
Hypercoordinated diorganoantimony(III) compounds of types [2‐(Me2NCH2)C6H4]2SbL and [PhCH2N(CH2C6H4)2]SbL (L = Cl, ONO2, OSO2CF3). Synthesis, structure and catalytic behaviour in the Henry reaction
Authors: Şuteu Răzvan , Raţ Ciprian I. , Silvestru Cristian , Simion Andrada , Candu Natalia , Pârvulescu Vasile I. , Silvestru Anca
Published: January 2020

The compounds [2‐(Me2NCH2)C6H4]2SbL (L = ONO2 (2), OSO2CF3 (3)) and [PhCH2N(CH2C6H4)2]SbL (L = ONO2 (5), OSO2CF3 (6)) were prepared by reacting [2‐(Me2NCH2)C6H4]2SbCl (1) and [PhCH2N(CH2C6H4)2]SbCl (4), respectively, with the appropriate silver(I) salt in a 1:1 molar ratio. The new species 2–6 were structurally characterized in solution using multinuclear NMR and in the solid state using infrared spectroscopy. The solid‐state structures for compounds 2, 4 and 6, as well as for the hydrolysis ionic product [{2‐(Me2N+HCH2)C6H4}{2‐(Me2NCH2)C6H4}SbOH][CF3SO3]− (3h) were determined using single‐crystal X‐ray diffraction. Medium to strong intramolecular N→ Sb interactions were observed in all these four compounds, thus resulting in hypercoordinated organoantimony(III) species 14‐Sb‐6 in 2 and 10‐Sb‐4 in the cation of 3h and in 4 and 6. Compounds 1–6 and the starting amines PhCH2NMe2 and PhCH2N(CH2C6H4Br‐2)2 were investigated as catalysts in the Henry (nitroaldol) addition of nitromethane to benzaldehyde. The activity of compounds 1–6 resulted as an effect of the cooperation of the positively charged antimony with the negatively charged nitrogen.
Properties of bamboo flour/high‐density polyethylene composites reinforced with ultrahigh molecular weight polyethylene
Authors: Guo Yong , Wang Li , Wang Hao , Chen Yuxia , Zhu Shiliu , Chen Tong , Luo Panpan
Published: January 2020

In order to improve the properties of bamboo‐plastic composites (BPCs), bamboo flour/high‐density polyethylene (HDPE) composites were reinforced with ultrahigh molecular weight polyethylene (UHMWPE). The effects of UHMWPE on properties of composites were studied. The crystallinity of composites decreased slightly. Compared with non‐UHMWPE added bamboo powder/HDPE composite, the composite with 6 wt % UHMWPE, showed decrease in water absorption to 0.41%, whereas its tensile strength and flexural strength increased to 34.51 and 25.88 MPa, respectively, a corresponding increase of 34.59 and 12.87%. The temperatures corresponding to initial degradation temperature (Tinitial) and maximum degradation temperature (Tmax) of the composite increased from 282.7 and 467.4 °C to 288.5 and 474.7 °C respectively. Scanning electron microscopic images showed that UHMWPE was well dispersed and fully extended as long fibers in the composite, forming a “three‐dimensional physically cross‐linked network structure,” which contributed to the improved properties of the composites. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2020,137, 48971.
Synthesis and rapid cement hardening evaluation of polycarboxylate superplasticizers incorporating ester groups in their backbone chain
Authors: Yu Peitao , Pang Hao , Huang Jianheng , Meng Yeyun , Huang Hao , Li Simin , Liao Bing , Liang liyan
Published: January 2020

A new water‐soluble, hydrolyzable polyethylene glycol di‐mercaptoacetate (PGM) was synthesized as a chain transfer agent. Subsequently, an early‐strength polycarboxylate superplasticizer (ESPC) was successfully prepared by using PGM as a chain transfer agent, along with acrylic acid, sodium methylallyl sulfonate (SMAS), and isoprene oxy poly(ethylene glycol) as comonomers. The effect of the ESPC on cement particles was systematically investigated. The fluidity, setting time, and compressive strength were measured to evaluate the performance of the ESPC and compared with those of a conventional polycarboxylate superplasticizer (PCE). The setting time of the ESPC can be shortened by 40 min in comparison with the PCE, and the compressive strength at 24 hr of setting time is increased by 5 MPa. In addition, X‐ray diffraction, thermogravimetric analysis, and scanning electron microscopy characterization were performed to investigate the effect of the ESPC on cement hydration from a microscopic level. Furthermore, the hydration heat was determined to investigate the interactions between the ESPC with the cement particles. It was found that if ester groups were introduced into the backbone chain of the ESPC and subsequently hydrolyzed, the ESPC was readily adsorbed onto cement particles. This enhanced adsorption improved the microstructure of the cement hydrate and accelerated the cement hydration process.
Benthic communities in the Southwest Atlantic Ocean: Conservation value of animal forests at the Burdwood Bank slope
Authors: Schejter Laura , Genzano Gabriel , Gaitán Esteban , Perez Carlos D. , Bremec Claudia S.
Published: January 2020

The characterization of benthic communities at the Burdwood Bank slope (≥200 m depth) is provided, comprising data from the marine protected area (MPA) Namuncurá II (created in December 2018), as well as from some deep bathyal surrounding areas in the Southwest Atlantic Ocean. This information was acquired during two research cruises with RV Puerto Deseado (Argentina) during 2016 and 2017.

Marine animal forests were detected in the study area: coral gardens, mainly composed of alcyonaceans, were detected in the south and west of Burdwood Bank (MPA Namuncurá II) and neighbouring areas, whereas pennatulacean aggregations were detected in the north‐west of the plateau. The three‐dimensional structures of live but also dead corals provide substrate and refuge to many associated species. Benthic communities dominated by sponges were also recorded between 200 and 300 m in depth.

Six sites that meet the characteristics of vulnerable marine ecosystems (VMEs) are reported.

Conservation strategies applied to scarcely known austral Argentinean waters led to the establishment of a pioneer MPA (Namuncurá I). Following the management plan that aimed to establish the biodiversity of Namuncurá I and neighbouring areas, the area of protection has now been enlarged to include the southern slope of the bank (currently Namuncurá II), where marine animal forests were detected, at depths below 200 m. The data presented here provide empirical evidence to support the conservation value of the region.
Maternal hypoxia developmentally programs low podocyte endowment in male, but not female offspring
Authors: Gonçalves Gessica D. , Walton Sarah L. , Gazzard Sarah E. , van der Wolde James , Mathias Paulo C. F. , Moritz Karen M. , Cullen‐McEwen Luise A. , Bertram John F.
Published: January 2020

Fetal hypoxia is a common complication of pregnancy. We have previously reported that maternal hypoxia in late gestation in mice gives rise to male offspring with reduced nephron number, while females have normal nephron number. Male offspring later develop proteinuria and renal pathology, including glomerular pathology, whereas female offspring are unaffected. Given the central role of podocyte depletion in glomerular and renal pathology, we examined whether maternal hypoxia resulted in low podocyte endowment in offspring. Pregnant CD1 mice were allocated at embryonic day 14.5 to normoxic (21% oxygen) or hypoxic (12% oxygen) conditions. At postnatal day 21, kidneys from mice were immersion fixed, and one mid‐hilar slice per kidney was immunostained with antibodies directed against p57 and synaptopodin for podocyte identification. Slices were cleared and imaged with a multiphoton microscope for podometric analysis. Male hypoxic offspring had significantly lower birth weight, nephron number, and podocyte endowment than normoxic male offspring (podocyte number; normoxic 62.86 ± 2.26 podocytes per glomerulus, hypoxic 53.38 ± 2.25; p < .01, mean ± SEM). In contrast, hypoxic female offspring had low birth weight but their nephron and podocyte endowment was the same as normoxic female offspring (podocyte number; normoxic 62.38 ± 1.86 podocytes per glomerulus, hypoxic 61.81 ± 1.80; p = .88). To the best of our knowledge, this is the first report of developmentally programmed low podocyte endowment. Given the well‐known association between podocyte depletion in adulthood and glomerular pathology, we postulate that podocyte endowment may place offspring at risk of renal disease in adulthood, and explain the greater vulnerability of male offspring.
Modeling and analysis of system reliability using phase‐type distribution closure properties
Authors: Alkaff Abdullah , Qomarudin Mochamad Nur
Published: January 2020

Phase‐type distribution closure properties are utilized to devise algorithms for generating reliability functions of systems with basic structures. These structures include series, parallel, K‐out‐of‐N, and standby structures with perfect/imperfect switch. The algorithms form a method for system reliability modeling and analysis based on the relationship between the system lifetime and component lifetimes for general structures. The proposed method is suitable for functional system reliability analysis, which can produce reliability functions of systems with independent components instead of only system reliability values. Once the system reliability function is obtained, other reliability measures such as the system's hazard function and mean time to failure can be obtained efficiently using only matrix algebra. Dimensional and numerical comparisons with computerized symbolic processing are also presented to show the superiority of the proposed method.
Identifying Language and Cognitive Profiles in Children With ASD via a Cluster Analysis Exploration: Implications for the New ICD‐11
Authors: Silleresi Silvia , Prévost Philippe , Zebib Racha , Bonnet‐Brilhault Fédérique , Conte Donatello , Tuller Laurice
Published: January 2020

The new version of the International Classification of Diseases (ICD‐11) mentions the existence of four different profiles in the verbal part of the Autism Spectrum Disorder (ASD), describing them as combinations of either spared or impaired functional language and intellectual abilities. The aim of the present study was to put ASD heterogeneity to the forefront by exploring whether clear profiles related to language and intellectual abilities emerge when investigation is extended to the entire spectrum, focusing on verbal children. Our study proposed a systematic investigation of both language (specifically, structural language abilities) and intellectual abilities (specifically, nonverbal cognitive abilities) in 51 6‐ to 12‐year‐old verbal children with ASD based on explicitly motivated measures. For structural language abilities, sentence repetition and nonword repetition tasks were selected; for nonverbal cognitive abilities, we chose Raven's Progressive Matrices, as well as Matrix Reasoning and Block Design from the Wechsler Scales. An integrative approach based on cluster analyses revealed five distinct profiles. Among these five profiles, all four logically possible combinations of structural language and nonverbal abilities mentioned in the ICD‐11 were detected. Three profiles emerged among children with normal language abilities and two emerged among language‐impaired children. Crucially, the existence of discrepant profiles of abilities suggests that children with ASD can display impaired language in presence of spared nonverbal intelligence or spared language in the presence of impaired nonverbal intelligence, reinforcing the hypothesis of the existence of a separate language module in the brain. Autism Res 2020, 13: 1155‐1167. © 2020 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Summary

The present work put Autism Spectrum Disorder heterogeneity to the forefront by exploring whether clear profiles related to language and cognitive abilities emerge when investigation is extended to the entire spectrum (focusing on verbal children). The use of explicitly motivated measures of both language and cognitive abilities and of an unsupervised machine learning approach, the cluster analysis, (a) confirmed the existence of all four logically possible profiles evoked in the new ICD‐11, (b) evoked the existence of (at least) a fifth profile of language/cognitive abilities, and (c) reinforced the hypothesis of a language module in the brain.
Sulfur and nitrogen co‐doped graphene quantum dot‐assisted chemiluminescence for sensitive detection of tryptophan and mercury (II)
Authors: Li Yue , Wang Jia , Yang Yaqiong , Han Suqin
Published: January 2020

A simple one‐step thermal treatment to prepare strong fluorescent sulfur and nitrogen co‐doped graphene quantum dots (SN‐GQD) using citric acid and l‐cysteine as precursors was developed. The ultra‐weak chemiluminescence (CL) from the reaction of hydrogen peroxide (H2O2) and periodate (IO4−) was significantly enhanced by SN‐GQD in acidic medium. The enhanced CL was induced by excited‐state SN‐GQD (SN‐GQD*), which was produced from the transfer energy of (O2)2* and 1O2 to SN‐GQD and recombination of oxidant‐injected holes and electrons in SN‐GQD. In the presence of tryptophan (Trp), the CL intensity of the SN‐GQD–H2O2–KIO4 system was greatly diminished. This finding was used to design a novel method for determination of Trp in the linear range 0.6–20.0 μM, with a limit of detection (LOD) of 58.0 nM. Furthermore, Hg2+ was detectable in the range 0.1–9.0 μM with a LOD of 64.0 nM, based on its marked enhancement of the SN‐GQD–H2O2–KIO4 CL system. The proposed method was successfully applied to detect Trp in milk and human plasma samples and Hg2+ in drinking water samples, with recoveries in the range 95.7–107.0%.
Different FDG‐PET metabolic patterns of anti‐AMPAR and anti‐NMDAR encephalitis: Case report and literature review
Authors: Wei Yi‐Chia , Tseng Jing‐Ren , Wu Chia‐Lun , Su Feng‐Chieh , Weng Wei‐Chieh , Hsu Chih‐Chin , Chang Kai‐Hsiang , Wu Chun‐Feng , Hsiao Ing‐Tsung , Lin Ching‐Po
Published: January 2020

Introduction

18F‐fluorodeoxyglucose (FDG)‐PET metabolic patterns of brain differ among autoimmune encephalitis with different neuronal surface antigens. In this case report, we compared the topographical relationship of cerebral glucose metabolism and antigen distribution in the patients with anti‐NMDAR and anti‐AMPAR encephalitis. Literature review summarized the common features of brain metabolism of autoimmune encephalitis.

Methods

The cerebral glucose metabolism was evaluated by FDG‐PET/CT during acute‐to‐subacute stage of autoimmune encephalitis and after treatment. The stereo and quantitative analysis of cerebral metabolism used standardized z‐score and visualized on three‐dimensional stereotactic surface projection. To map NMDAR and AMPAR in human brain, we adopted genetic atlases from the Allen Institute and protein atlases from Zilles's receptor densities.

Results

The three‐dimensional stereotactic surface projection displayed frontal‐dominant hypometabolism in a 66‐year‐old female patient with anti‐AMPAR encephalitis and occipital‐dominant hypometabolism in a 29‐year‐old female patient with anti‐NMDAR encephalitis. Receptor density maps revealed opposite frontal–occipital gradients of AMPAR and NMDAR, which reflect reduced metabolism in the correspondent encephalitis. FDG‐PET hypometabolic areas possibly represent receptor hypofunction with spatial correspondence to receptor distributions of the autoimmune encephalitis. The reversibility of hypometabolism was in line with patients' cognitive improvement. The literature review summarized six features of metabolic anomalies of autoimmune encephalitis: (a) temporal hypermetabolism, (b) frontal hypermetabolism and (c) occipital hypometabolism in anti‐NMDAR encephalitis, (d) hypometabolism in association cortices, (e) sparing of unimodal primary motor cortex, and (e) reversibility in recovery.

Conclusions

The distinct cerebral hypometabolic patterns of autoimmune encephalitis were representative for receptor hypofunction and topographical distribution of antigenic receptors. The reversibility of hypometabolism marked the clinical recovery of autoimmune encephalitis and made FDG‐PET of brain a valuable diagnostic tool.
Exploring factors relating to extinction disclosures: What motivates companies to report on biodiversity and species protection?
Authors: Hassan Abeer Mohamed , Roberts Lee , Atkins Jill
Published: January 2020

This paper seeks to contribute to the existing business strategy and the environment literature by investigating the disclosure practices of biodiversity/extinction (B/E) and threatened species. We use greenwashing theory to understand global companies' motivation to report on B/E information. Data are collected from 200 Fortune Global companies for 3 years. We develop our comprehensive 53 disclosure index and create and test OLS regression model to measure the relationships between B/E disclosures and its determinants factors including environmental performance, industry sector, country, assurance, environmental awards, presence of biodiversity partners, and the number of species' related disclosure. Our results reveal that there are positive significant relationships between B/E disclosure and assurance provided by the Big 4: gaining an environmental award, companies from high biodiversity risk sectors, developing countries, presence of biodiversity partners, and how many specific biodiversity words are published in companies' reports. On the other hand, there are positive insignificant relationships between B/E disclosure and assurance: poor performers and the number of species disclosed in companies' reports. Our findings have important implications for regulators and policymakers. Our evidence appears to be robust when controlling for possible endogeneities.
Integrating circular business models and development tools in the circular economy transition process: A firm‐level framework
Authors: Chen Li‐Heng , Hung Peiying , Ma Hwong‐wen
Published: January 2020

Along with the concept of circular economy growing worldwide, circular business models (CBMs) have been receiving ever greater attention in both the business sector and academia. However, the existing literature on the CBM is scattered and fragmented; this study offers an integrated firm‐level framework to link CBM typologies, the circular economy transition process, and relevant tools for CBM development and clarifies the positioning and roles of those tools in the process. In response to the fragmentation issue, results of this study are presented in three subtopics: (a) CBM typologies and archetypes, (b) transition guidelines, and (c) major analytical tools for CBM research. The roles and functions of CBM typologies and tools were integrated in different stages of the transition process, and the challenges and shortfalls for CBM research in the various stages were identified. This work lays the foundation for future operational studies.
Perspectives of people with mental health problems at hot spots: Attitudes and perceptions of safety, crime, and the police
Authors: Goldberg Victoria , White Clair , Weisburd David
Published: January 2020

People who live in places with high levels of crime and disorder are more likely to experience mental illness compared with those who do not live in these types of place (Weisburd et al., 2018; Weisburd & White, 2019). The increased police presence on high crime streets may also increase the likelihood that these individuals will encounter law enforcement. There is a strong body of literature focused on the relationship between neighborhoods and the physical and mental health of residents (e.g. Arcaya et al., 2016; Duncan & Kawachi, 2018; Leventhal & Brooks‐Gunn, 2003), but there are very few studies that look at the perceptions of people with mental illness directly, particularly as they relate to the environment of the street on which they live and attitudes toward the police. In turn, existing studies generally look at the most serious mental health problems (e.g. schizophrenia), ignoring more common mental health concerns such as post‐traumatic stress disorder (PTSD) and depression. This paper uses self‐report data from a large in‐person survey of people who live on crime hot spot and non‐hot spot streets in order to assess attitudes among a broader group of persons with mental health problems. Furthermore, we examine the interaction between living in crime hot spots and non‐hot spots and perceptions of these residents. Our findings in this broader sample confirm earlier studies that identify greater fear and less trust of the police among persons with mental illnesses. At the same time, our findings suggest that fear of crime and perceptions of police are moderated by living in a crime hot spot.
Working with suicidal clients: Psychotherapists and allied professionals speak about their experiences
Authors: Scupham Susan , Goss Stephen P.
Published: January 2020

Objective

To ascertain the impact that working with suicidal clients has on health professionals.

Design

This research study used an online survey, which covered a broad range of questions in relation to the impact of working with suicidal clients.

Method

A total of 110 practitioners completed the online survey. The responses were analysed using descriptive statistics and thematic analysis.

Results

The findings highlighted how overwhelmed practitioners felt at the time of their client's death, expressing shock, sadness, anger, guilt and helplessness. In addition, the findings revealed that even several years later practitioners were still marked by the experience, expressing statements such as, ‘you don't forget’, ‘thinking about it produces a feeling of horror’ and ‘it creates anxiety and apprehension when I encounter similar patients’.

Conclusions

Analysis from a mixed‐methods, pluralist perspective suggests that there is no single answer to supporting practitioners when a client dies. The research highlights that continuing professional development providers and practitioners should understand that such reactions are to be expected, and therefore prepared for. Pressures of work and lack of time were particularly emphasised as negatively impacting on respondents’ ability to take appropriate measures for their own self‐care and ability to continue to practise effectively. It is our opinion that organisations that do not take this into account are operating in a way that is short‐sighted. This adds to the likelihood of potentially serious negative effects for the personal well‐being and professional functioning of the individual practitioners directly affected.
In‐situ Transmission Electron Microscope Techniques for Heterogeneous Catalysis
Authors: He Bowen , Zhang Yixiao , Liu Xi , Chen Liwei
Published: January 2020

The physicochemical properties of heterogeneous catalysts in static or inert environments often deviate greatly from the properties under in‐situ or working conditions. To gain an insightful understanding of realistic catalyst properties and the corresponding catalytic mechanisms, it is essential to identify and rationalize changes in catalysts under reaction conditions. In recent years, in‐situ transmission electron microscope (in‐situ TEM) techniques have been increasingly developed, offering a unique approach to visualize the evolution of heterogeneous catalysis with ultra‐high spatial resolution, good energy resolution and reasonable temporal resolution under controllable or even realistic catalytic conditions. In this review, we have summarized recent advances in the in‐situ TEM analysis of heterogeneous catalysis, which suggests the great potential of this technique in this important field. Furthermore, technical challenges and possible solutions are discussed.
Electrochemically Triggered Interfacial Deposition/Assembly of Aqueous‐Suspended Colloids
Authors: Iqbal Md. Shamim , Zhan Wei
Published: January 2020

Following our recent work on polyelectrolyte deposition on ferrocene‐terminated self‐assembled monolayers (Langmuir2018,34,12776–12786), we seek in this study to answer the following question: How would aqueous‐suspended colloids respond to the same electrochemical trigger – ferrocene oxidation? Using carboxylic‐terminated polystyrene nano‐/microbeads as a model colloid, we confirm first their transfer to and deposition at such redox‐active surfaces. Key factors involved, including the starting electrode surfaces, colloid size, range/duration of applied potential, and small supporting electrolytes, are examined in detail. A particularly interesting finding among these is the superior efficiency of the electrochemically triggered assembly compared to the electrically driven process. Taking advantage of this feature, we demonstrate fast, high‐fidelity colloid micropattern formation on electrodes at the end.
Manipulation of the Coordination Geometry along the C4 Rotation Axis in a Dinuclear Tb3+ Triple‐Decker Complex via a Supramolecular Approach
Authors: Katoh Keiichi , Yasuda Nobuhiro , Damjanović Marko , Wernsdorfer Wolfgang , Breedlove Brian K. , Yamashita Masahiro
Published: January 2020

A supramolecular complex (1⋅C60) was prepared by assembling (C60‐Ih)[5,6]fullerene (C60) with the dinuclear Tb3+ triple‐decker complex [(TPP)Tb(Pc)Tb(TPP)] (1: Tb3+=trivalent terbium ion, Pc2−=phthalocyaninato, TPP2−=tetraphenylporphyrinato) with quasi‐D4h symmetry to investigate the relationship between the coordination symmetry and single‐molecule magnet (SMM) properties. Tb3+‐Pc triple‐decker complexes (Tb2Pc3) have an important advantage over Tb3+‐Pc double‐decker complexes (TbPc2) since the magnetic relaxation processes correspond to the Zeeman splitting when there are two 4f spin systems. The two Tb3+ sites of 1 are equivalent, and the twist angle (φ) was determined to be 3.62°. On the other hand, the two Tb3+ sites of 1⋅C60 are not equivalent. The φ values for sites Tb1 and Tb2 were determined to be 3.67° and 33.8°, respectively, due to a change in the coordination symmetry of 1 upon association with C60. At 1.8 K, 1 and 1⋅C60 undergo different magnetic relaxations, and the changes in the ground state affect the spin dynamics. Although 1 and 1⋅C60 relax via QTM in a zero applied magnetic field (H), H dependencies of the magnetic relaxation times (τ) for H>1500 Oe are similar. On the other hand, for H<1500 Oe, the τ values have different behaviors since the off‐diagonal terms (
) affect the magnetic relaxation mechanism. From temperature (T) and H dependences of τ, spin‐phonon interactions along with direct and Raman mechanisms explain the spin dynamics. We believe that a supramolecular method can be used to control the magnetic anisotropy along the C4 rotation axis and the spin dynamic properties in dinuclear Ln3+‐Pc multiple‐decker complexes.
Cystobactamid 507: Concise Synthesis, Mode of Action, and Optimization toward More Potent Antibiotics
Authors: Elgaher Walid A. M. , Hamed Mostafa M. , Baumann Sascha , Herrmann Jennifer , Siebenbürger Lorenz , Krull Jana , Cirnski Katarina , Kirschning Andreas , Brönstrup Mark , Müller Rolf , Hartmann Rolf W.
Published: January 2020

Lack of new antibiotics and increasing antimicrobial resistance are among the main concerns of healthcare communities nowadays, and these concerns necessitate the search for novel antibacterial agents. Recently, we discovered the cystobactamids—a novel natural class of antibiotics with broad‐spectrum antibacterial activity. In this work, we describe 1) a concise total synthesis of cystobactamid 507, 2) the identification of the bioactive conformation using noncovalently bonded rigid analogues, and 3) the first structure–activity relationship (SAR) study for cystobactamid 507 leading to new analogues with high metabolic stability, superior topoisomerase IIA inhibition, antibacterial activity and, importantly, stability toward the resistant factor AlbD. Deeper insight into the mode of action revealed that the cystobactamids employ DNA minor‐groove binding as part of the drug–target interaction without showing significant intercalation. By designing a new analogue of cystobactamid 919‐2, we finally demonstrated that these findings could be further exploited to obtain more potent hexapeptides against Gram‐negative bacteria.
Three‐Coordinate Rhodium Complexes in Low Oxidation States
Authors: Varela‐Izquierdo Víctor , López José A. , de Bruin Bas , Tejel Cristina , Ciriano Miguel A.
Published: January 2020

The isolation of simultaneously low‐coordinate and low‐valent compounds is a timeless challenge for preparative chemists. This work showcases the preparation and full characterization of tri‐coordinate rhodium(‐I) and rhodium(0) complexes as well as a rare rhodium(I) complex. Reduction of [{Rh(μ‐Cl)(IPr)(dvtms)}2] (1, IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolyl‐2‐ylidene; dvtms=divinyltetramethyldisiloxane) with KC8 gave the trigonal complexes K[Rh(IPr)(dvtms)] and [Rh(IPr)(dvtms)], whereas the cation [Rh(IPr)(dvtms)]+ results from their oxidation or by abstraction of chloride from 1 with silver salts. The paramagnetic Rh0 complex is a unique fully metal‐centered radical with the unpaired electron in the dz2 orbital. The Rh(‐I) complex reacts with PPh3 with replacement of the NHC ligand, and behaves as a nucleophile, which upon reaction with [AuCl(PPh3)] generates the trigonal pyramidal complex [(IPr)(dvtms)Rh‐Au(PPh3)] with a metal–metal bond between two d10 metal centers.
Real textile wastewater treatment using nano graphene‐based materials: Optimum pH, dosage, and kinetics for colour and turbidity removal
Authors: de Araújo Caroline M. B. , Oliveira do Nascimento Gabriel F. , Bezerra da Costa Gabriel R. , Baptisttella Ana M. S. , Fraga Tiago J. M. , de Assis Filho Romero B. , Ghislandi Marcos G. , da Motta Sobrinho Mauricio A.
Published: January 2020

Textile effluent is one of the most hazardous types of wastewater for both the environment and human health when discharged without proper treatment. This work stands out as one of the first to evaluate the parameters for the application of graphene oxide (GO) to treat real textile wastewater. A comparative analysis was conducted to investigate the removal efficiencies of turbidity and apparent colour from raw textile wastewater using GO. The effects of different parameters, such as GO dosage, pH, and contact time were discussed, considering a removal mechanism based on the salting out effect. Results regarding treatment using GO followed by centrifugation showed that in >1 hour nearly 90% turbidity was decreased, and an apparent colour removal efficiency over 76% was recorded, which is twice the value obtained with the conventional treatment applied in textile mills. Over 60% chemical oxygen demand was reduced. Tests using GO followed by sedimentation also revealed promising results, showing removal efficiencies of 66% and 88% for apparent colour and turbidity, respectively. These results suggest that GO could be promising for real wastewater treatment.
Oscillatory power number, power density model, and effect of restriction size for a moving‐baffle oscillatory baffled column using CFD modelling
Authors: Sutherland Kayte , Pakzad Leila , Fatehi Pedram
Published: January 2020

Although single‐hole oscillatory columns have been studied since the 1990s, to this day there is an absence of appropriate dimensionless groups to express the hydrodynamic conditions and power requirement for the moving‐baffle oscillatory baffled column (OBC). This paper uses computational fluid dynamic (CFD) software coupled with moving overset meshing to aid in the derivation of the first dimensionless oscillatory power number for OBCs. In terms of the moving‐baffle OBC, this work marks the first time a power density equation has been derived specifically to account for this column's unique hydrodynamic profile. Equations for period‐averaged Reynolds number and period‐averaged Strouhal numbers were developed to better estimate the fluid intensity within these moving‐baffle columns. This work serves as an example of how complex and challenging flow regimes, such as periodically oscillating flow, can be simplified and analyzed to produce appropriate design equations.
Survival of African American and non‐Hispanic white men with prostate cancer in an equal‐access health care system
Authors: Riviere Paul , Luterstein Elaine , Kumar Abhishek , Vitzthum Lucas K. , Deka Rishi , Sarkar Reith R. , Bryant Alex K. , Bruggeman Andrew , Einck John P. , Murphy James D. , Martínez María Elena , Rose Brent S.
Published: January 2020

Background

African American (AA) men in the general US population are more than twice as likely to die of prostate cancer (PC) compared with non‐Hispanic white (NHW) men. The authors hypothesized that receiving care through the Veterans Affairs (VA) health system, an equal‐access medical system, would attenuate this disparity.

Methods

A longitudinal, centralized database of >20 million veterans was used to assemble a cohort of 60,035 men (18,201 AA men [30.3%] and 41,834 NHW men [69.7%]) who were diagnosed with PC between 2000 and 2015.

Results

AA men were more likely to live in regions with a lower median income ($40,871 for AA men vs $48,125 for NHW men;P < .001) and lower high school graduation rates (83% for AA men vs 88% for NHW men;P < .001). At the time of diagnosis, AA men were younger (median age, 63.0 years vs 66.0 years;P < .001) and had a higher prostate‐specific antigen level (median, 6.7 ng/mL vs 6.2 ng/mL;P < .001), but were less likely to have Gleason score 8 to 10 disease (18.8% among AA men vs 19.7% among NHW men;P < .001), a clinical T classification ≥3 (2.2% vs 2.9%;P < .001), or distant metastatic disease (2.7% vs 3.1%;P = 0.01). The 10‐year PC‐specific mortality rate was slightly lower for AA men (4.4% vs 5.1%;P = .005), which was confirmed in multivariable competing‐risk analysis (subdistribution hazard ratio, 0.85; 95% CI, 0.78‐0.93;P < .001).

Conclusions

AA men diagnosed with PC in the VA health system do not appear to present with more advanced disease or experience worse outcomes compared with NHW men, in contrast to national trends, suggesting that access to care is an important determinant of racial equity.
Near‐Infrared Electrochemiluminescence from Bistridentate Ruthenium(II) Di(quinoline‐8‐yl)pyridine Complexes in Aqueous Media
Authors: Majuran Mayoorini , Armendariz‐Vidales Georgina , Carrara Serena , Haghighatbin Mohammad A. , Spiccia Leone , Barnard Peter J. , Deacon Glen B. , Hogan Conor F. , Tuck Kellie L.
Published: January 2020

We report the synthesis, photophysics, electrochemistry and electrochemiluminescence (ECL) of two dqp (dqp=2,6‐di(quinoline‐8‐yl)pyridine) based ruthenium(II) complexes, bearing either a n‐butyl ester (1) or the corresponding carboxylic acid functionality (2). The complexes were prepared from [Ru(dqp)(MeCN)3][PF6]2 by reaction with the dqp precursor using microwave irradiation. In both cases, photoluminescence spectra present strong 3MLCT‐based red/near‐infrared (NIR) emissions centred at about 710 nm. The photoluminescence quantum yields were 6.1 % and 1.8 % for 1 and 2 respectively while the excited state lifetimes were 3.60 μs and 2.37 μs. Both complexes are ECL active, although ECL efficiency (ΦECL) of 1 was substantially higher than 2, due to its more favourable electrochemical properties. Importantly, 1 also gave strong ECL in aqueous media, which is rare for near‐infrared emitters. The results suggest the possibility of very interesting ECL sensing applications for this class of emitter in biological media.
Synthesis of 2′‐Fluorinated Northern Methanocarbacyclic (2′‐F‐NMC) Nucleosides and Their Incorporation Into Oligonucleotides
Authors: Akabane‐Nakata Masaaki , Kumar Pawan , Erande Namrata D. , Matsuda Shigeo , Manoharan Muthiah
Published: January 2020

This article describes chemical synthesis of 2′‐fluorinated Northern methanocarbacyclic (2′‐F‐NMC) nucleosides and phosphoramidites, based on a bicyclo[3.1.0]hexane scaffold bearing all four natural nucleobases (U, C, A, and G), and their incorporation into oligonucleotides by solid‐supported synthesis. This synthesis starts from commercially available cyclopent‐2‐en‐1‐one to obtain the fluorinated carbocyclic pseudosugar intermediate (S.13), which can be converted to the uridine intermediate by condensation with isocyanate, followed by cyclization, and to adenine and guanine precursors by microwave‐assisted reactions. All four 2′‐F‐NMC phosphoramidites are synthesized from S.13 in a convergent approach, and the monomers are used for synthesis of 2′‐F‐NMC‐modified oligonucleotides. © 2020 by John Wiley & Sons, Inc.

Basic Protocol 1: Preparation of fluorinated carbocyclic pseudosugar intermediate

Basic Protocol 2: Preparation of 2′‐F‐NMC uridine and cytidine phosphoramidites

Basic Protocol 3: Preparation of 2′‐F‐NMC adenosine phosphoramidite

Basic Protocol 4: Preparation of 2′‐F‐NMC guanosine phosphoramidite

Basic Protocol 5: Synthesis of oligonucleotides containing 2ʹ‐F‐NMC
Investigating Memory Updating in Mice Using the Objects in Updated Locations Task
Authors: Wright Destiny S. , Bodinayake Kasuni K. , Kwapis Janine L.
Published: January 2020

In the laboratory, memory is typically studied as a de novo experience, in which a naïve animal is exposed to a discrete learning event that is markedly different from its past experiences. Most real‐world memories, however, are updates—modifications or additions—to existing memories. This is particularly true in the aging, experienced brain. To better understand memory updating, we have developed a new behavioral paradigm called the objects in updated locations (OUL) task. OUL relies on hippocampus‐dependent spatial learning and has the advantage of being able to test both the original memory and the updated information in a single test session. Further, OUL relies on incidental learning that avoids unnecessary stress that might hinder the performance of aging animals. In OUL, animals first learn the location of two identical objects in a familiar context. This memory is then updated by moving one object to a new location. Finally, to assess the animals’ memory for the original and the updated information, all animals are given a test session in which they are exposed to four copies of the object: two in the original training locations, one in the updated location, and one in a novel location. By comparing exploration of the novel location to the familiar locations, we can infer whether the animal remembers the original and updated object locations. OUL is a simple but powerful task that could provide new insights into the cellular, circuit‐level, and molecular mechanisms that support memory updating. © 2020 by John Wiley & Sons, Inc.
Agents of change: Women in top management and corporate environmental performance
Authors: Burkhardt Kirsten , Nguyen Pascal , Poincelot Evelyne
Published: January 2020

We analyze the influence of gender diversity in top management on the environmental performance of French firms. Consistent with gender socialization theory, which posits that women are raised from childhood to be more nurturing and compassionate for others, we find that firms with more women in top management exhibit higher environmental performance. This result extends those already reported in the literature regarding the effect of gender diversity at board level. We also show that women in top management are associated with several key indicators such as development of eco‐friendly products and commitment to resource reduction. Furthermore, we find that the influence of women is weaker in firms with a lower environmental performance and in firms with high‐growth opportunities because these firms are likely to prioritize their own development. This suggests, in line with social role theory, that women also adapt into the role that organizations expect from them.
Impact of facies and diagenetic variability on permeability and fluid flow in an oolitic grainstone—Pleistocene Miami Oolite
Authors: Harris Paul (Mitch) , Purkis Sam
Published: January 2020

The Miami Oolite of South Florida is representative of a grainstone‐rich carbonate unit that has been surficially karsted, and therefore may be considered as an analogue for subsurface reservoirs/aquifers with ‘high’ permeability extremes. The deposit can potentially serve to improve a conceptual understanding of heterogeneity as imparted by shallow‐marine facies changes and early meteoric diagenetic modification. Reviewed here are recent studies of the Miami Oolite with the intent to emphasize those key aspects of the facies and early diagenesis that most impact permeability and fluid flow. The Miami Oolite displays the preserved morphology of a fossilized ooid sandbody, even though it has been subaerially exposed in a tropical climate since its deposition approximately 120 kyr bp during the last interglacial highstand. The depositional motif is one of a dip‐oriented, tidal bar belt of shoals and shallow channels fronted by a strike‐oriented barrier bar. The barrier bar comprises cross‐stratified grainstones and locally burrowed grain/packstones, while the tidal shoals and channels are more commonly burrowed pack/grainstones. Surficial karst features (dolines and stratiform caves) have been added during the ca 120 kyr of subaerial exposure, but of more significance is the associated solution‐enhancement of the widespread burrowed facies. Since the Miami Oolite is the uppermost portion of the Biscayne Aquifer, there is also an understanding of fluid flow through the deposit that sheds valuable insight on the larger scale, shallow subsurface plumbing. The pore system comprises matrix pores (interparticle and separate vugs) and touching‐vug macropores that are commonly associated with burrowed [Ophiomorpha] intervals. Ground‐penetrating radar, well and flow test data indicate that matrix porosity provides most of the groundwater storage, whereas the touching vug macropores account for the majority of flow. The dolines and shallow caves seem to be sufficiently spaced as to generally not be in direct connection, with the result that they are less important in terms of regional flow than the prevailing pore system.
The Catalan butterfly monitoring scheme has the capacity to detect effects of modifying agricultural practices
Authors: Lee Marina S. , Comas Jordi , Stefanescu Constantí , Albajes Ramon
Published: January 2020

Impacts of agricultural management practices on the receiving environment are seldom suitably assessed because environmental monitoring is costly. In this regard, data generated by already existing environmental survey networks (ESNs) may have sufficient capacity to detect effects. Here, we study the capacity of the Catalan butterfly monitoring scheme (CBMS) to detect differences in butterfly abundance due to changes in agricultural practices. As a model, we compared butterfly abundance across two landscape types according to agricultural intensification. A 2 km diameter buffer area was centered on the CBMS transect, the control group were transects located in areas where intensive agriculture represented <20% of the area; a treated group was simulated by selecting transects located in areas where intensive agriculture occupied an area over 40%. The Welch t‐test (α = 0.05 and 80% power) was used to compare butterfly abundance per section across landscape types. The capacity of the t‐test to detect changes in mean butterfly abundance, of 12 butterfly indicators relevant to farmland, was calculated annually and for 5‐, 10‐, and 15‐yr periods. Detection capacity of the t‐test depended mainly on butterfly data sample size and variability; difference in butterfly abundance was less important. The t‐test would be capable of detecting acceptably small population changes across years and sites. For instance, considering a 15‐yr period, it would be possible to detect a change in abundance below 10% of the multispecies indicators (all butterfly species, open habitat species, mobile species, and grassland indicators) and two single species (Lasiommata megera and Lycaena phlaeas). When comparisons were carried out within each year, the t‐test would only be capable of detecting a change below 30% for all butterfly species, mobile species, and L. megera. However, detection capacity rapidly improved with the addition of further years, and with 5 yr of monitoring, all indicators but Thymelicus acteon had a detection capacity below 30%. We therefore conclude that, from a statistical point of view, the CBMS data “as is” are sensitive enough for monitoring effects of changes in agricultural practices. It could be used, for instance, for the general surveillance of genetically modified crops.