bluuebunny/crossref_metadata_2025 huggingface dataset:
Spoof Localized Surface Plasmons for Sensing Applications
Authors: Zhang Xuanru , Cui Wen Yi , Lei Yi , Zheng Xin , Zhang Jingjing , Cui Tie Jun
Published: February 2021

Localized surface plasmons (LSPs) are localized oscillations of free electrons in metal nanoparticles at optical frequencies. Confined mode profiles and near‐field enhancements make LSPs ultrasensitive to the dielectric environment, making them good candidates as sensors. The concept and applications have been generalized to spoof LSPs in microwave and terahertz frequencies, via plasmonic metamaterials composed of subwavelength corrugations. Herein, the basic physics, sensing prototypes, detection schemes, and state‐of‐the‐art progress are broadly reviewed from optical LSP sensing to microwave spoof LSP sensing. While optical LSPs exhibit localized sensitivity enhancement with high attenuation, spoof LSPs in microwave and terahertz frequencies combine the characteristics of deep‐subwavelength confinement and sensitivity enhancement of optical LSPs with low loss, high quality factor, multipole modes, and on‐chip detection of optical microcavities. Meanwhile, advances in printed circuits, integrated circuits, wireless communications, wearable devices, and Internet of things have endowed microwave sensing with a solid technical foundation and promising prospects. Applications in liquid sensing, gas sensing, and wearable sensing are demonstrated. Discussions are extended to electromagnetic sensing throughout the wave spectra, with concerns about key supporting technologies. The prospect of microwave sensing is emphatically investigated, specifically on leveraging the advantages of plasmonic enhancement.
Programming Multistate Aggregation‐Induced Emissive Polymeric Hydrogel into 3D Structures for On‐Demand Information Decryption and Transmission
Authors: Qiu Huiyu , Wei Shuxin , Liu Hao , Zhan Beibei , Yan Huizhen , Lu Wei , Zhang Jiawei , Wu Si , Chen Tao
Published: February 2021

Fluorescent hydrogels have recently become one of the most prominent materials for smart confidential information protection. But it is still quite challenging to develop a 3D anticounterfeiting platform with on‐demand information decryption and transmission capacities, which are of great importance to achieve high‐level data protection security. Herein, robust aggregation‐induced emissive polymeric hydrogels with thermo‐triggered multistate fluorescence switching, shape memory, and self‐healing properties based on supramolecular dynamic lanthanide coordination interactions are presented. By a collective action of these promising properties, a fluorescent hydrogel‐based 3D information encoding platform is demonstrated for on‐demand information decryption, in which information pre‐encrypted in 3D hydrogel structures is stepwise decrypted by the control of external stimuli. Such unique on‐demand information decryption features are further expanded to the transmission of manifold customized messages to multiple receivers. Herein, the possibility of utilizing 3D fluorescent hydrogel structures for high‐level information encryption and on‐demand decryption is opened up.
Fetal early motor neuron disruption and prenatal molecular diagnosis in a severe BICD2‐opathy
Authors: Marchionni Enrica , Agolini Emanuele , Mastromoro Gioia , Guadagnolo Daniele , Coppola Giulia , Roggini Mario , Riminucci Mara , Novelli Antonio , Giancotti Antonella , Corsi Alessandro , Pizzuti Antonio
Published: February 2021

BICD2 (BICD Cargo Adaptor 2, MIM*609797) mutations are associated with severe prenatal‐onset forms of spinal muscular atrophy, lower extremity‐predominant 2B (SMALED2B MIM 618291) or milder forms with childhood‐onset (SMALED2A MIM 615290). Etiopathogenesis is not fully clarified and a wide spectrum of phenotypic presentations is reported, ranging from extreme prenatal forms with adverse outcome, to slow progressive late‐onset forms. We report a fetus at 22 gestational weeks with evidence of Arthrogryposis Multiplex Congenita on ultrasound, presenting with fixed extended lower limbs and flexed upper limbs, bilateral clubfoot and absent fetal movements. A trio‐based prenatal Exome Sequencing was performed, disclosing a de novo heterozygous pathogenic in frame deletion (NM_015250.3: c.1636_1638delAAT; p.Asn546del) in BICD2. After pregnancy termination, quantitative analysis on NeuN immunostained spinal cord sections of the ventral horns, revealed that neuronal density was markedly reduced compared to the one of an age‐matched normal fetus and an age‐matched type‐I Spinal Muscular Atrophy sample, used as a comparative model. The present case, the first prenatally diagnosed and neuropathologically characterized, showed an early motor neuron loss in SMALED2B, providing further insight into the pathological basis of BICD2‐opathies.
Later Stone Age human hair from Vaalkrans Shelter, Cape Floristic Region of South Africa, reveals genetic affinity to Khoe groups
Authors: Coutinho Alexandra , Malmström Helena , Edlund Hanna , Henshilwood Christopher S. , van Niekerk Karen L. , Lombard Marlize , Schlebusch Carina M. , Jakobsson Mattias
Published: February 2021

Previous studies show that the indigenous people of the southern Cape of South Africa were dramatically impacted by the arrival of European colonists starting ~400 years ago and their descendants are today mixed with Europeans and Asians. To gain insight on the occupants of the Vaalkrans Shelter located at the southernmost tip of Africa, we investigated the genetic make‐up of an individual who lived there about 200 years ago. We further contextualize the genetic ancestry of this individual among prehistoric and current groups. From a hair sample excavated at the shelter, which was indirectly dated to about 200 years old, we sequenced the genome (1.01 times coverage) of a Later Stone Age individual. We analyzed the Vaalkrans genome together with genetic data from 10 ancient (pre‐colonial) individuals from southern Africa spanning the last 2000 years. We show that the individual from Vaalkrans was a man who traced ~80% of his ancestry to local southern San hunter–gatherers and ~20% to a mixed East African‐Eurasian source. This genetic make‐up is similar to modern‐day Khoekhoe individuals from the Northern Cape Province (South Africa) and Namibia, but in the southern Cape, the Vaalkrans man's descendants have likely been assimilated into mixed‐ancestry “Coloured” groups. The Vaalkrans man's genome reveals that Khoekhoe pastoralist groups/individuals lived in the southern Cape as late as 200 years ago, without mixing with non‐African colonists or Bantu‐speaking farmers. Our findings are also consistent with the model of a Holocene pastoralist migration, originating in Eastern Africa, shaping the genomic landscape of historic and current southern African populations.
The effect of high wear diets on the relative pulp volume of the lower molars
Authors: Selig Keegan R. , Kupczik Kornelius , Silcox Mary T.
Published: February 2021

Objectives

One role of dental pulp is in the upkeep and maintenance of dentine. Under wear, odontoblasts in the pulp deposit tertiary dentine to ensure the sensitive internal dental tissues are not exposed and vulnerable to infection. It follows that there may be an adaptive advantage for increasing molar pulp volume in anthropoid primate taxa that are prone to high levels of wear. The relative volume of dental pulp is therefore predicted to covary with dietary abrasiveness (in the sense of including foods that cause high degrees of wear).

Materials and Methods

We examined relatively unworn lower second molars in pairs of species of extant hominoids, cebids, and pitheciids that vary in the abrasiveness of their diet (n = 36). Using micro‐CT scans, we measured the percent of tooth that is pulp (PTP) as the ratio of pulp volume to that of the total volume of the tooth.

Results

We found that in each pair of species, the taxa that consume a more abrasive diet had a significantly higher PTP than the closely related taxa that consume a softer diet.

Conclusions

Our results point to an adaptive mechanism in the molars of taxa that consume abrasive diets and are thus subject to higher levels of wear. Our results provide additional understanding of the relationship between dental pulp and diet and may offer insight into the diet of extinct taxa such as Paranthropus boisei or into the adaptive context of the taurodont molars of Neanderthals.
Selectively Upgrading Lignin Derivatives to Carboxylates through Electrochemical Oxidative C(OH)−C Bond Cleavage by a Mn‐Doped Cobalt Oxyhydroxide Catalyst
Authors: Zhou Hua , Li Zhenhua , Xu Si‐Min , Lu Lilin , Xu Ming , Ji Kaiyue , Ge Ruixiang , Yan Yifan , Ma Lina , Kong Xianggui , Zheng Lirong , Duan Haohong
Published: February 2021

Oxidative cleavage of C(OH)−C bonds to afford carboxylates is of significant importance for the petrochemical industry and biomass valorization. Here we report an efficient electrochemical strategy for the selective upgrading of lignin derivatives to carboxylates by a manganese‐doped cobalt oxyhydroxide (MnCoOOH) catalyst. A wide range of lignin‐derived substrates with C(OH)‐C or C(O)‐C units undergo efficient cleavage to corresponding carboxylates in excellent yields (80–99 %) and operational stability (200 h). Detailed investigations reveal a tandem oxidation mechanism that base from the electrolyte converts secondary alcohols and their derived ketones to reactive nucleophiles, which are oxidized by electrophilic oxygen species on MnCoOOH from water. As proof of concept, this approach was applied to upgrade lignin derivatives with C(OH)‐C or C(O)‐C motifs, achieving convergent transformation of lignin‐derived mixtures to benzoate and KA oil to adipate with 91.5 % and 64.2 % yields, respectively.
Biomimetic Nanoemulsion for Synergistic Photodynamic‐Immunotherapy Against Hypoxic Breast Tumor
Authors: Zhang Yifan , Liao Yunyan , Tang Qinan , Lin Jing , Huang Peng
Published: February 2021

Photodynamic therapy (PDT) is commonly used as an “in situ vaccine” to enhance the response rate of PD‐1/PD‐L1 antibodies. Unfortunately, the high cost and adverse effects of these antibodies, and the hypoxic state of solid tumors limits the efficacy of synergistic photodynamic‐immunotherapy. Here, we developed a biomimetic nanoemulsion camouflaged with a PD‐1‐expressing cell membrane for synergistic photodynamic‐immunotherapy against hypoxic breast tumors. The perfluorocarbon of the nanoemulsion could provide oxygen as the source of PDT against hypoxic tumors. Moreover, co‐delivering a photosensitizer and the PD‐1 protein (substituting for a PD‐L1 antibody) achieves the synergy effect of PDT and immunotherapy. Synergistic photodynamic‐immunotherapy completely inhibited primary and distant subcutaneous 4T1 tumors, mechanistically by boosting the maturation of dendritic cells and tumor infiltration of cytotoxic T lymphocytes.
Catalytic Enantioselective Desymmetrizing Fischer Indolization through Dynamic Kinetic Resolution
Authors: Ghosh Biki , Balhara Reena , Jindal Garima , Mukherjee Santanu
Published: February 2021

The first catalytic enantioselective Fischer indolization of prochiral diketones containing enantiotopic carbonyl groups is developed and shown to proceed through dynamic kinetic resolution (DKR). Catalyzed by the combination of a spirocyclic chiral phosphoric acid and ZnCl2 (Lewis acid assisted Brønsted acid), this direct approach combines 2,2‐disubstituted cyclopentane‐1,3‐diones with N‐protected phenylhydrazines to furnish cyclopenta[b]indole derivatives containing an all‐carbon quaternary stereocenter with good to excellent enantioselectivities.
Enantioselective Synthesis of Pyroglutamic Acid Esters from Glycinate via Carbonyl Catalysis
Authors: Ma Jiguo , Zhou Qinghai , Song Guanshui , Song Yongchang , Zhao Guoqing , Ding Kuiling , Zhao Baoguo
Published: February 2021

Direct α‐functionalization of NH2‐free glycinates with relatively weak electrophiles such as α,β‐unsaturated esters still remains a big challenge in organic synthesis. With chiral pyridoxal 5 d as a carbonyl catalyst, direct asymmetric conjugated addition at the α‐C of glycinate 1 a with α,β‐unsaturated esters 2 has been successfully realized, to produce various chiral pyroglutamic acid esters 4 in 14–96 % yields with 81–97 % ee's after in situ lactamization. The trans and cis diastereomers can be obtained at the same time by chromatography and both of them can be easily converted into chiral 4‐substituted pyrrolidin‐2‐ones such as Alzheimer's drug Rolipram (11) with the same absolute configuration via tert‐butyl group removal and subsequent Barton decarboxylation.
Stabilization of Polynitrogen Anions in Tantalum–Nitrogen Compounds at High Pressure
Authors: Bykov Maxim , Bykova Elena , Ponomareva Alena V. , Abrikosov Igor A. , Chariton Stella , Prakapenka Vitali B. , Mahmood Mohammad F. , Dubrovinsky Leonid , Goncharov Alexander F.
Published: February 2021

The synthesis of polynitrogen compounds is of great importance due to their potential as high‐energy‐density materials (HEDM), but because of the intrinsic instability of these compounds, their synthesis and stabilization is a fundamental challenge. Polymeric nitrogen units which may be stabilized in compounds with metals at high pressure are now restricted to non‐branched chains with an average N−N bond order of 1.25, limiting their HEDM performances. Herein, we demonstrate the synthesis of a novel polynitrogen compound TaN5 via a direct reaction between tantalum and nitrogen in a diamond anvil cell at circa 100 GPa. TaN5 is the first example of a material containing branched all‐single‐bonded nitrogen chains [N55−]∞. Apart from that we discover two novel Ta–N compounds: TaN4 with finite N44− chains and the incommensurately modulated compound TaN2−x, which is recoverable at ambient conditions.
π‐Interpenetrated 3D Covalent Organic Frameworks from Distorted Polycyclic Aromatic Hydrocarbons
Authors: Martínez‐Abadía Marta , Strutyński Karol , Lerma‐Berlanga Belén , Stoppiello Craig T. , Khlobystov Andrei N. , Martí‐Gastaldo Carlos , Saeki Akinori , Melle‐Franco Manuel , Mateo‐Alonso Aurelio
Published: February 2021

Three‐dimensional covalent organic frameworks (3D COFs) with a pcu topology have been obtained from distorted polycyclic aromatic hydrocarbons acting as triangular antiprismatic (D3d) nodes. Such 3D COFs are six‐fold interpenetrated as the result of interframework π‐stacking, which enable charge transport properties that are not expected for 3D COFs.
A Solid‐State Intramolecular Wittig Reaction Enables Efficient Synthesis of Endofullerenes Including Ne@C60, 3He@C60, and HD@C60
Authors: Hoffman Gabriela , Walkey Mark C. , Gräsvik John , Bacanu George R. , Alom Shamim , Bloodworth Sally , Light Mark E. , Levitt Malcolm H. , Whitby Richard J.
Published: February 2021

An open‐cage fullerene incorporating phosphorous ylid and carbonyl group moieties on the rim of the orifice can be filled with gases (H2, He, Ne) in the solid state, and the cage opening then contracted in situ by raising the temperature to complete an intramolecular Wittig reaction, trapping the atom or molecule inside. Known transformations complete conversion of the product fullerene to C60 containing the endohedral species. As well as providing an improved synthesis of large quantities of 4He@C60, H2@C60, and D2@C60, the method allows the efficient incorporation of expensive gases such as HD and 3He, to prepare HD@C60 and 3He@C60. The method also enables the first synthesis of Ne@C60 by molecular surgery, and its characterization by crystallography and 13C NMR spectroscopy.
Chiral Mesostructured NiO Films with Spin Polarisation
Authors: Bai Te , Ai Jing , Liao Liyang , Luo Junwei , Song Cheng , Duan Yingying , Han Lu , Che Shunai
Published: February 2021

Spin polarisation is found in the centrosymmetric nonferromagnetic crystals, chiral mesostructured NiO films (CMNFs), fabricated through the symmetry‐breaking effect of a chiral molecule. Two levels of chirality were identified: primary nanoflakes with atomically twisted crystal lattices and secondary helical stacking of the nanoflakes. Spin polarisation of the CMNFs was confirmed by chirality‐dependent magnetic‐tip conducting atomic force microscopy (mc‐AFM) and magnetic field‐independent magnetic circular dichroism (MCD). Electron transfer in the symmetry‐breaking electric field was speculated to create chirality‐dependent effective magnetic fields. The asymmetric spin–orbit coupling (SOC) generated by effective magnetic fields selectively modifies the opposite spin motion in the antipodal CMNFs. Our findings provide fundamental insights for directional spin control in unprecedented functional inorganic materials.
Electrochemical Characterization of Single Layer Graphene/Electrolyte Interface: Effect of Solvent on the Interfacial Capacitance
Authors: Wu Yih‐Chyng , Ye Jianglin , Jiang Gengping , Ni Kun , Shu Na , Taberna Pierre‐Louis , Zhu Yanwu , Simon Patrice
Published: February 2021

The development of the basic understanding of the charge storage mechanisms in electrodes for energy storage applications needs deep characterization of the electrode/electrolyte interface. In this work, we studied the charge of the double layer capacitance at single layer graphene (SLG) electrode used as a model material, in neat (EMIm‐TFSI) and solvated (with acetonitrile) ionic liquid electrodes. The combination of electrochemical impedance spectroscopy and gravimetric electrochemical quartz crystal microbalance (EQCM) measurements evidence that the presence of solvent drastically increases the charge carrier density at the SLG/ionic liquid interface. The capacitance is thus governed not only by the electronic properties of the graphene, but also by the specific organization of the electrolyte side at the SLG surface originating from the strong interactions existing between the EMIm+ cations and SLG surface. EQCM measurements also show that the carbon structure, with the presence of sp2 carbons, affects the charge storage mechanism by favoring counter‐ion adsorption on SLG electrode versus ion exchange mechanism in amorphous porous carbons.
Structure controlled Au@Pd NPs/rGO as robust heterogeneous catalyst for Suzuki coupling in biowaste‐derived water extract of pomegranate ash
Authors: Appa Rama Moorthy , Raghavendra Padmasale , Lakshmidevi Jangam , Naidu Bandameeda Ramesh , Sarma Loka Subramanyam , Venkateswarlu Katta
Published: February 2021

This article explores the aptness of water extract of pomegranate ash (WEPA) of agro‐waste origin as an effective media for a heterogeneous reduced graphene oxide (rGO)‐supported Au–Pd bimetallic nanoparticles (NPs)‐catalyzed Suzuki coupling without the need of additional ligand, base, and additives at room temperature. Morphological and structural details of Au–Pd bimetallic nanoparticles/rGO are evaluated using a suite of electron microscopy, X‐ray diffraction, and cyclic voltammetry techniques. A facile chemical reduction method using methyl amine borane as a reducing agent yields 5.8 nm‐sized Au–Pd bimetallic particles on the rGO surface with an Au@Pd core‐shell morphology. The structural, synergistic, and support capabilities offered by core‐shell structured Au@Pd NPs/rGO could made a positive contribution in achieving Suzuki coupling reactions in very short times (5–30 min) with a good to excellent yields of biaryls (91–99%). The catalyst has been easily recovered by phase separation and reused for three consecutive times without losing its effective catalytic property up to two cycles.
Thermal and mechanical properties of epoxy resin reinforced with modified iron oxide nanoparticles
Authors: Baghdadi Yasmine N. , Youssef Lucia , Bouhadir Kamal , Harb Mohammad , Mustapha Samir , Patra Digambara , Tehrani‐Bagha Ali Reza
Published: February 2021

Epoxy polymers, having good mechanical properties and thermal stability, are often used for engineering applications. Their properties can be further enhanced by the addition of iron oxide (Fe3O4) nanoparticles (NPs) as fillers to the resin. In this study, pristine Fe3O4 NPs were functionalized with polydopamine (PDA), (3‐glycidoxypropyl)trimethoxysilane (GPTMS), and (3‐aminopropyl)trimethoxysilane (APTES). X‐ray diffraction and scanning electron microscopy (SEM) were used to study any changes in the crystal structure and size of the NPs while Fourier‐Transform Infrared Spectroscopy (FTIR) and Thermogravimetric Analysis (TGA) were used to ensure the presence of functional groups on the surface. The mechanical properties of the Fe3O4‐based nanocomposites generally improved except when reinforced with Fe3O4/PDA. The maximum improvement in tensile strength (∼34%) and fracture toughness (∼13%) were observed for pristine Fe3O4‐based nanocomposites. Dynamic mechanical analysis (DMA) showed that the use of any of the treated NPs improved the material's initial storage modulus and had a substantial impact on its dissipation potential. Also, it was observed that the glass transition temperature measurements by DMA and differential scanning calorimetry were below that of pure epoxy. SEM of the cracked surfaces shows that the incorporation of any NPs leads to an enhancement in its thermal and mechanical properties.
Neuronal cell types in the anterior ventral thalamic nucleus of the camel
Authors: Al‐Hussain Saleh M. , Albostanji Shaden A. , Mustafa Ayman G. , Zaqout Sami
Published: February 2021

The anterior ventral nucleus neurons in of the camel brain were morphologically studied by Golgi impregnation method. Two neuronal types of were found in the camel anterior ventral thalamic nucleus, namely, Golgi‐type I neurons and Golgi‐type II neurons. Those neurons were generally similar to their counterparts in the human thalamus. The Golgi‐type I neurons exhibited medium to large cell body (mean diameter = 25 μm) which was either multipolar or triangular in shape. They had from 3 to 10 primary dendrites with many branches but with no spines or appendages. The Golgi‐type II neurons had small to medium size (somatic mean diameter = 17.5 μm), their cell bodies were variable in shape, some were round, and others were multipolar or fusiform. These cells bodies had two to six primary dendrites with few branches that may have spines and/or grape‐like appendages. Our findings shed some light on the anterior ventral thalamic nucleus structure of the camel as one of the strongest adaptive mammals to the hard climatic conditions.
Implementation of two‐field inflation for cosmic linear anisotropy solving system
Authors: Morales‐Martínez Braulio , Arciniega Gustavo , Jaime Luisa G. , Piccinelli Gabriella
Published: February 2021

We outline the modifications in the numerical Boltzmann code Cosmic Linear Anisotropy Solving System (CLASS) in order to include extra inflationary fields. The functioning of the code is first described, how and where modifications are meant to be done are later explained. In the present study, we focus on the modifications needed for the implementation of a two‐field inflationary model, with canonical kinetic terms and a polynomial potential with no cross terms, presenting preliminary results for the effect of the second field on the spectra. The adaptability of the code is exploited, making use of the classes and structures of C and the generic Runge–Kutta integration tool provided by the program.
Deconfinement phase transition under chemical equilibrium
Authors: Dexheimer Veronica , Aryal Krishna , Wolf Madison , Constantinou Constantinos , Farias Ricardo L. S.
Published: February 2021

In this work, we investigate how the assumption of chemical equilibrium with leptons affects the deconfinement phase transition to quark matter. This is carried out within the framework of the Chiral Mean Field model allowing for nonzero net strangeness, corresponding to the conditions found in astrophysical scenarios. We build three‐dimensional quantum chromodynamics phase diagrams with temperature, baryon chemical potential, and either charge or isospin fraction or chemical potential to show how the deconfinement region collapses to a line in the special case of chemical equilibrium, such as the one established in the interior of cold catalyzed neutron stars.
Differential Item Functioning Based on Autism Features, IQ, and Age on the Screen for Child Anxiety Related Disorders (SCARED) Among Youth on the Autism Spectrum
Authors: Schiltz Hillary K. , Magnus Brooke E.
Published: February 2021

Anxiety commonly occurs among youth on the autism spectrum, yet measurement of anxiety in this population is complicated by a number of factors, including potentially overlapping symptomatology, the child's intellectual functioning, and changes in anxiety across development. Moreover, few studies have examined the psychometric properties of anxiety measures in this population, and no study to date has tested whether there are systematic differences in the measurement of anxiety, or differential item functioning (DIF), across the high degree of heterogeneity and the developmental course of autism. To test this possibility, data were combined across multiple studies using the National Database for Autism Research, an NIH‐funded data repository. Parent‐report on the Screen for Child Anxiety Related Disorders (SCARED) and Social Communication Questionnaire (SCQ) were used as measures of anxiety and autism features, respectively. A confirmatory factor analysis indicated good fit of the literature standard five‐factor structure. Moderated nonlinear factor analysis (MNLFA) revealed multiple items with intercept and loading DIF based on level of autism features, IQ, and age, especially for items related to social behavior. Therefore, although the measure's factor structure is consistent with that found in the general population, the SCARED may not capture differences in anxiety equivalently for all children on the spectrum and across their development. Clinicians and researchers need to be especially vigilant in measuring anxiety symptoms in children with autism by removing items flagged for DIF from the SCARED and/or by using multiple measures and informants.

Lay Abstract

Autistic youth often experience clinical levels of anxiety. Many tools used to measure anxiety were developed for the general population, but not for use with autistic youth. This study found that the Screen for Child Anxiety Related Disorders (SCARED) measures the same five dimensions of anxiety as in the general population. Parents, however, may respond differently to questions on the SCARED based on their child's autism features, intellectual functioning, and age, which impacts our ability to accurately measure anxiety among autistic youth.
Oxidatively Induced Reductive Elimination for Methyl Group Transfer via Isolable Transmetalation Complexes
Authors: Kim Jinwoo , Jin Seongho , Kim Dongwook , Chang Sukbok
Published: February 2021

Herein, we describe the mechanistic details on the oxidatively induced reductive elimination of isolated methyl iridium and ruthenium metallacycle complexes. It was demonstrated that the otherwise challenging C─C bond formation is indeed facilitated by external oxidation, being enabled under mild conditions. Computational analyses supported the proposed high‐valent pathway, where the energy barrier for reductive elimination significantly decreases upon the metallic oxidation to facilitate the desired C─C bond formation.
Inhibition of emotions in healthy aging: age‐related differences in brain network connectivity
Authors: Almdahl Ina S. , Martinussen Liva J. , Agartz Ingrid , Hugdahl Kenneth , Korsnes Maria S.
Published: February 2021

Introduction

Successful inhibition of distracting emotions is important for preserving well‐being and daily functioning. There is conflicting evidence regarding the impact of healthy aging on emotional inhibition, and possible age‐related alterations in the neuronal underpinnings of emotional interference processing are unexplored.

Methods

Thirty younger (mean age 26 years; 15 women) and 30 older (mean age 71 years; 13 women) healthy adults performed a face–word emotional Stroop task while undergoing functional magnetic resonance imaging of the brain. A resting‐state scan was acquired for calculating the amplitude of low‐frequency fluctuations as an estimate of vascular reactivity. Comparisons of brain activation during the task were assessed in a whole‐brain, voxel‐wise analysis, contrasting congruent, and incongruent conditions. The canonical regions of the frontoparietal, salience, dorsal attention, and default mode networks were used as seed regions for assessing functional connectivity within and between large‐scale brain networks. Task performance was evaluated using response accuracy and response time.

Results

The older adults had longer response times and lower task accuracy than the younger adults, but the emotional interference effect was not significantly different between the groups. Whole‐brain analysis revealed no significant age‐related differences in brain activation patterns. Rescaling the data for estimated variability in vascular reactivity did not affect the results. In older adults, there was relatively stronger functional connectivity with the default mode network, the sensorimotor network, and the dorsal attention network for the frontoparietal and salience network seeds during the task. Conversely, younger adults had relatively stronger connections within and between the frontoparietal and salience networks.

Conclusion

In this first fMRI study of emotional Stroop interference in older and younger adults, we found that the emotional interference effect was unchanged in healthy aging and replicated the finding from non‐emotional task studies that older adults have greater between‐network and less within‐network connectivity compared to younger adults.
Climate adaptation within the tourism sector of a small island developing state: A case study from the coastal accommodations subsector in the Bahamas
Authors: Pathak Arsum , van Beynen Philip E. , Akiwumi Fenda A. , Lindeman Kenyon C.
Published: February 2021

Tourism in Small Island Developing States (SIDS) is vulnerable to climate change. Using the Bahamas as a case study, this study presents findings from a survey administered with property managers from the coastal accommodations sector to identify their adaptation strategies to tackle climate change. We also evaluate their adaptive capacity by developing SIDS‐specific indicators based on a capitals approach. Findings indicate that efforts toward adaptation were limited to disaster preparedness for hurricanes, reflecting a short‐term focus in the face of climate change uncertainties. In addition to the lack of finances and knowledge for incorporating adaptation measures, their capacity to adapt is diminished due to a lack of access to climate change information, skilled staff, and specific climate change planning reflecting limited human and institutional capitals. Recommendations are provided for strategies synergistic with the resilience focus of our paper such as ecosystem‐based adaptation and green jobs. The study informs tourism resilience and adaptation planning in the Bahamas which may apply to other SIDS.
Supplier evaluation in the context of circular economy: A forward step for resilient business and environment concern
Authors: Haleem Abid , Khan Shahbaz , Luthra Sunil , Varshney Harshit , Alam Musaib , Khan Mohd Imran
Published: February 2021

Resource depletion is a concern for the global economy; many think that available resources on the planet will not be able to cater to an ever‐growing population. Thus, economies are trying to become circular, leaving behind the linear tradition linear approach. In the circular economy (CE), physical resources and energy are made to loop back into the supply chain (SC) for a more extended period. Proper selection of suppliers is an essential criterion towards proper execution of the CE principle in SC. In this research, we have constructed a framework for evaluating the supplier concerning the CE implementation. Further, this research identifies the criterion and sub‐criterion, which are pertinent for evaluating the supplier in CE context. Fuzzy‐based ‘Criteria Importance Through Inter‐Criteria Correlation (CRITIC)’ method is justifiably applied to determine the aggregated weights of the criteria. Finally, ‘Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS)’ method is used to determine the suppliers' ranking in the Indian automobile industry. Six criteria and 24 sub‐criteria are obtained as per recent literature and then inputs from experts. ‘Environment’ criterion came out as the most favourable criterion with a subjective weight of 0.230. The current research is one of the first such attempts to provide criteria for supplier selection in a CE environment. The developed framework would help organisations in implementing CE‐based supplier selection. The identified criteria and sub‐criteria would provide organisations with means to evaluate suppliers and help suppliers develop an effective and efficient CE based on the SC.
Thinking differently about family violence: Shifting from a criminal justice response to a recovery orientation
Authors: Roguski Michael , Edge Kiri
Published: February 2021

Against a backdrop of increasing rates of family violence in Aotearoa New Zealand, opportunities exist to reflect upon, and critically evaluate, our conventional understanding and responses to family violence. In doing so, there is considerable potential to further develop and progress more efficacious orientations and approaches. The current study sought to explore alternative approaches from the perspectives of 35 men who have engaged in family violence; understanding the type of supports and interventions that have aided their desistance. Participants traced their desistance to family violence to communities of support, communities that have raised awareness of family violence while simultaneously engaging men who either use violence or were at risk of using violence, and the development of holistic, therapeutic, and supportive communities. Themes from these men's narratives highlight the benefits of a move away from a criminogenic response to a community‐embedded recovery orientation.
A Review on Glassy and Rubbery Polymeric Membranes for Natural Gas Purification
Authors: Farnam Marjan , bin Mukhtar Hilmi , bin Mohd Shariff Azmi
Published: February 2021

A comprehensive overview of membrane technology used for natural gas purification and other gas separation applications including methods, materials, and results described in previous studies is presented. Different membrane categories are elaborated thoroughly followed by comparisons made between glassy and rubbery polymeric membranes. Various approaches to improve membrane separation performance, such as incorporation of inorganic fillers and blending technique, are discussed. Gas separation in different membranes, e.g., glassy/rubbery polymer blend membranes, mixed matrix membranes, and polymeric blend mixed matrix membranes, are considered. Adopted techniques by researchers to solve existing issues in membrane fabrication and performance are explained in detail.
Arylphosphonate‐Tethered Porphyrins: Fluorescence Silencing Speaks a Metal Language in Living Enterocytes**
Authors: Keil Claudia , Klein Julia , Schmitt Franz‐Josef , Zorlu Yunus , Haase Hajo , Yücesan Gündoğ
Published: February 2021

We report the application of a highly versatile and engineerable novel sensor platform to monitor biologically significant and toxic metal ions in live human Caco‐2 enterocytes. The extended conjugation between the fluorescent porphyrin core and metal ions through aromatic phenylphosphonic acid tethers generates a unique turn off and turn on fluorescence and, in addition, shifts in absorption and emission spectra for zinc, cobalt, cadmium and mercury. The reported fluorescent probes p‐H8TPPA and m‐H8TPPA can monitor a wide range of metal ion concentrations via fluorescence titration and also via fluorescence decay curves. Cu‐ and Zn‐induced turn off fluorescence can be differentially reversed by the addition of common chelators. Both p‐H8TPPA and m‐H8TPPA readily pass the mammalian cellular membrane due to their amphipathic character as confirmed by confocal microscopic imaging of living enterocytes.
Mucopolysaccharidosis (MPS): Review of the literature and case series of five pediatric dental patients
Authors: Hirst Lorna , Mubeen Suhaym , Abou‐Ameira Gehan , Chakrapani Anupam
Published: February 2021

Patients with MPS present with a plethora of dental manifestations, accompanying behavioral difficulties and medical comorbidities which often dictate the need for treatment in specialist centers. Prevention is therefore mandatory in this high‐risk group.
Mechanistic Insights for Nitromethane Activation into Reactive Nitrogenating Reagents
Authors: Qu Zheng‐Wang , Zhu Hui , Grimme Stefan
Published: February 2021

Recently, it was found that nitromethane (CH3NO2) can be activated into a useful nitrogenating reagent for the synthesis of amide and nitrile compounds. In this work, the mechanisms of CH3NO2 activation are explored in detail by extensive DFT calculations. In aqueous triflic acid (HOTf) solution, the formal 1,3‐H‐shift of CH3NO2 into transient CH2=NO2H is identified as the rate‐limiting step over a barrier of 29.6 kcal/mol, followed by multistep acid hydrolysis to cleave the C=N bond to form NH3OH+ (and HCOOH) as final product. In contrast, in non‐aqueous acetic acid (AcOH) solution with electrophilic Tf2O and nucleophilic HCOOH additives, the C=N bond is cleaved by sequential steps of H2O elimination, electrophilic Tf2O activation, nucleophilic HCOOH addition and acetate/TfO− exchange, affording AcONH3+ as more reactive nitrogenating reagent for Beckmann‐type reactions.
Thermally Responsive Poly(ethylene oxide)‐Based Polyrotaxanes Bearing Hydrogen‐Bonding Pillar[5]arene Rings**
Authors: Kato Kenichi , Onishi Katsuto , Maeda Koki , Yagyu Masafumi , Fa Shixin , Ichikawa Takahiro , Mizuno Motohiro , Kakuta Takahiro , Yamagishi Tada‐aki , Ogoshi Tomoki
Published: February 2021

Poly(ethylene oxide)s (PEOs) are useful polymers with good water solubility, biological compatibility, and commercial availability. PEOs with various end groups were threaded into pillar[5]arene rings in a mixture of water and methanol to afford pseudopolyrotaxanes. Corresponding polyrotaxanes were also constructed by capping COOH‐terminated pseudopolyrotaxanes with bulky amines, in which multiple hydrogen bonds involving the pillar[5]arene OH groups were critically important to prevent dethreading. The number of threaded ring components could be rationally controlled in these materials, providing a simple and versatile method to tune the mechanical and thermal properties. Specifically, a polyrotaxane with a high‐molecular‐weight axle became elastic upon heating above the melting point of PEOs and exhibited temperature‐dependent shape memory property because of the topological confinement and crosslinked hydrogen bonds.
Legionellen im Kühlwasser kontinuierlich ermitteln
Authors: Ohme Holger , Becker Jennifer , Jahn Pascal , Heinecke Dirk
Published: February 2021

Ein neu entwickeltes Messgerät kann innerhalb weniger Stunden alle Legionellen Arten in einer Wasserprobe (Legionella spp. = species pluralis) bestimmen. Für technische Wassersysteme aus denen Aerosole ausgetragen werden können, bedeutet diese Möglichkeit eines zuverlässigen Schnelltests einen entscheidenden Fortschritt.
Die Pumpe macht's
Authors: Hüttemann Udo
Published: February 2021

Mit dem Lean Lab hat BASF am Standort Münster ein hochmodernes, modulares Laborkonzept für die Herstellung von Fahrzeuglacken realisiert. Im Vordergrund stehen dabei digitalisierte und transparente Entwicklungsprozesse sowie ein hohes Maß an Ressourceneff
Teaching and Learning Scientific Inquiry – Step by Step
Authors: Sommer Katrin , Kring Petra , Strippel Christian Georg , Emmerich Katharina
Published: February 2021

Naturwissenschaftliche Erkenntnisgewinnung ist ein zentraler Kompetenzbereich des Chemieunterrichts. Das Herzstück stellt der Weg der Erkenntnisgewinnung dar. Für die reflektierte Nutzung des Weges der Erkenntnisgewinnung ist die Vermittlung von deklarativem Wissen über die einzelnen Schritte nötig. Wie Studien nahelegen, sollte dieses Methodenwissen explizit vermittelt werden. Das hier präsentierte Vermittlungskonzept zeigt für jeden Schritt die Bedeutung auf dem Weg der Erkenntnisgewinnung auf, benennt die Merkmale des Schrittes (Methodenwissen) und wendet das Methodenwissen in Form eines Merkmalschecks auf ein lehrplanrelevantes, experimentelles Beispiel an. Das unterstreicht die enge Verzahnung von Denkweisen (Methodenwissen) und Arbeitsweisen (Fachmethoden). Damit liegt erstmals ein Vermittlungskonzept für den Chemieunterricht der Sekundarstufe I vor, das den Weg der Erkenntnisgewinnung selbst zum Lernziel macht.
Improving Strategies in the Development of Protein‐Downregulation‐Based Antiandrogens
Authors: Zhang Rongyu , Huang Chenchao , Xiao Xiaohui , Zhou Jinming
Published: February 2021

The androgen receptor (AR) plays a crucial role in the occurrence and development of prostate cancer (PCa), and its signaling pathway remains active in castration‐resistant prostate cancer (CRPC) patients. The resistance against antiandrogen drugs in current clinical use is a major challenge for the treatment of PCa, and thus the development of new generations of antiandrogens is under high demand. Recently, strategies for downregulating the AR have attracted significant attention, given its potential in the discovery and development of new antiandrogens, including G‐quadruplex stabilizers, ROR‐γ inhibitors, AR‐targeting proteolysis targeting chimeras (PROTACs), and other selective AR degraders (SARDs), which are able to overcome current resistance mechanisms such as acquired AR mutations, the expression of AR variable splices, or overexpression of AR. This review summarizes the various strategies for downregulating the AR protein, at either the mRNA or protein level, thus providing new ideas for the development of promising antiandrogen drugs.
Risk assessment for distant metastasis in differentiated thyroid cancer using molecular profiling: A matched case‐control study
Authors: Yip Linwah , Gooding William E. , Nikitski Alyaksandr , Wald Abigail I. , Carty Sally E. , Karslioglu‐French Esra , Seethala Raja R. , Zandberg Dan P. , Ferris Robert L. , Nikiforova Marina N. , Nikiforov Yuri E.
Published: February 2021

Background

Risk stratification for patients with differentiated thyroid cancer (DTC) is based primarily on pathologic tumor characteristics. Accurate preoperative prognostication could allow for more informed initial surgical recommendations, particularly among patients at a higher risk for distant metastasis (DM). The objective of this study was to characterize the genetic profile of DTC with DM and to validate a molecular‐based risk stratification.

Methods

A case‐control study design was used to analyze patients who had DTC with DM (n = 62) and a propensity matched cohort of patients who had DTC without DM after at least 5 years of follow‐up using the ThyroSeq version 3 targeted next‐generation sequencing assay. The results were classified into high‐risk, intermediate‐risk, and low‐risk of aggressive disease.

Results

Most patients who had DTC with DM (66%) had a late‐hit mutation in TERT, TP53, or PIK3CA. After propensity matching by age, tumor size, and sex, the high‐risk molecular profile had strong association with DM (high‐risk vs intermediate‐risk: odds ratio, 25.1; 95% CI, 3.07‐204.4; P < .001; high‐risk vs low‐risk: odds ratio, 122.5; 95% CI, 14.5‐1038.4; P < .001). Overall, molecular risk categories were associated with DM risk, with a concordance index of 0.836 (95% CI, 0.759‐0.913), which remained consistent after internal validation. Within the range of 5% to 10% of DM observed in DTC, the expected probability of DM would be 0.2% to 0.4% for the low‐risk molecular profile, 4.7% to 9.4% for the intermediate‐risk molecular profile, and 19.3% to 33.5% for the high‐risk molecular profile.

Conclusions

In this matched case‐control study, genetic profiling using an available molecular assay provided accurate and robust risk stratification for DM in patients with DTC. The availability of preoperative prognostication may allow tailoring treatment for patients with DTC.
DiPOSH: A portable OpenSHMEM implementation for short API‐to‐network path
Authors: Coti Camille , Malony Allen D.
Published: February 2021

In this article, we introduce DiPOSH, a multi‐network, distributed implementation of the OpenSHMEM standard. The core idea behind DiPOSH is to have an API‐to‐network software stack as slim as possible, in order to minimize the software overhead. Following the heritage of its non‐distributed parent POSH, DiPOSH's communication engine is organized around the processes' shared heaps, and remote communications are moving data from and to these shared heaps directly. This article presents its architecture and several communication drivers, including one that takes advantage of a helper process, called the Hub, for inter‐process communications. This architecture allows use to explore different options for implementing the communication drivers, from using high‐level, portable, optimized libraries to low‐level, close to the hardware communication routines. We present the perspectives opened by this additional component in terms of communication scheduling between and on the nodes. DiPOSH is available athttps://github.com/coti/DiPOSH.
Monocyte CD169 expression in COVID‐19 patients upon intensive care unit admission
Authors: Ortillon Marine , Coudereau Remy , Cour Martin , Rimmelé Thomas , Godignon Marine , Gossez Morgane , Yonis Hodane , Argaud Laurent , Lukaszewicz Anne‐Claire , Venet Fabienne , Monneret Guillaume
Published: February 2021

During the second surge of COVID‐19 in France (fall 2020), we assessed the expression of monocyte CD169 (i.e., Siglec‐1, one of the numerous IFN‐stimulated genes) upon admission to intensive care units of 45 patients with RT‐PCR‐confirmed SARS‐CoV2 pulmonary infection. Overall, CD169 expression was strongly induced on circulating monocytes of COVID‐19 patients compared with healthy donors and patients with bacterial sepsis. Beyond its contribution at the emergency department, CD169 testing may be also helpful for patients' triage at the ICU to rapidly reinforce suspicion of COVID‐19 etiology in patients with acute respiratory failure awaiting for PCR results for definitive diagnosis.