bluuebunny/crossref_metadata_2025 huggingface dataset:
Importance of subterranean fungi in the diet of bonobos in Kokolopori
Authors: Lucchesi Stefano , Cheng Leveda , Wessling Erin G. , Kambale Bienfait , Lokasola Albert L. , Ortmann Sylvia , Surbeck Martin
Published: July 2021

Nonstaple food is a food resource which sole consumption does not allow the maintenance of regular physiological functions, thus constituting a minor portion of an individual's diet. Many primates consume nonstaple food such as meat, insects, and fungi. Hypotheses on the dietary importance of nonstaple food include its role as fallback food and as source of specific nutrients. We tested these two hypotheses by investigating mycophagy (i.e., the consumption of fungi) in a population of wild bonobos in the Kokolopori Bonobo Reserve, DRC. Specifically, we examined the relationship between fungus consumption and various factors relevant to bonobo feeding ecology (i.e., fruit abundance and the consumption of other food types). Additionally, we measured the deviation from linear travel when bonobos searched for fungi to evaluate the nature of fungus consumption (e.g., opportunistic or targeted). Lastly, we examined the nutritional content of the major fungus species consumed (Hysterangium bonobo) to test whether this food item was potentially consumed as source of specific nutrients. We found that bonobos spent a higher proportion of their time feeding on fungi when fruit abundance was higher, indicating that fungi were not consumed as a fallback food. Moreover, bonobos deviated from linear travel when visiting fungus patches more than observed when visiting fruit patches, suggesting that they actively sought out fungi. Lastly, initial analyses suggest that H. bonobo samples contained high concentration of sodium. Collectively, these results suggest that subterranean fungi appear to be attractive food source to Kokolopori bonobos, and that mycophagy may serve to supplement nutrients, like sodium, in bonobo diet.
Electrochemical Potential‐Driven High‐Throughput Molecular Electronic and Spintronic Devices: From Molecules to Applications
Authors: Gupta Ritu , Jash Priyajit , Sachan Pradeep , Bayat Akhtar , Singh Vikram , Mondal Prakash Chandra
Published: July 2021

Molecules are fascinating candidates for constructing tunable and electrically conducting devices by the assembly of either a single molecule or an ensemble of molecules between two electrical contacts followed by current‐voltage (I‐V) analysis, which is often termed “molecular electronics”. Recently, there has been also an upsurge of interest in spin‐based electronics or spintronics across the molecules, which offer additional scope to create ultrafast responsive devices with less power consumption and lower heat generation using the intrinsic spin property rather than electronic charge. Researchers have been exploring this idea of utilizing organic molecules, organometallics, coordination complexes, polymers, and biomolecules (proteins, enzymes, oligopeptides, DNA) in integrating molecular electronics and spintronics devices. Although several methods exist to prepare molecular thin‐films on suitable electrodes, the electrochemical potential‐driven technique has emerged as highly efficient. In this Review we describe recent advances in the electrochemical potential driven growth of nanometric various molecular films on technologically relevant substrates, including non‐magnetic and magnetic electrodes to investigate the stimuli‐responsive charge and spin transport phenomena.
Construction of Co–Mn Prussian Blue Analog Hollow Spheres for Efficient Aqueous Zn‐ion Batteries
Authors: Zeng Yinxiang , Lu Xue Feng , Zhang Song Lin , Luan Deyan , Li Sheng , Lou Xiong Wen (David)
Published: July 2021

Prussian blue analogs (PBAs) are considered as reliable and promising cathode materials for aqueous Zn‐ion batteries (AZIBs), but they suffer from low capacity and poor cycling stability due to insufficient active sites and structural damage caused by the ion insertion/extraction processes. Herein, a template‐engaged ion exchange approach has been developed for the synthesis of Co‐substituted Mn‐rich PBA hollow spheres (CoMn‐PBA HSs) as cathode materials for AZIBs. Benefiting from the multiple advantageous features including hollow structure, abundant active sites, fast Zn2+ ion diffusion, and partial Co substitution, the CoMn‐PBA HSs electrode shows efficient zinc ion storage properties in terms of high capacity, decent rate capability and prolonged cycle life.
Au⋅⋅⋅H−C Hydrogen Bonds as Design Principle in Gold(I) Catalysis
Authors: Darmandeh Heidar , Löffler Julian , Tzouras Nikolaos V. , Dereli Busra , Scherpf Thorsten , Feichtner Kai‐Stephan , Vanden Broeck Sofie , Van Hecke Kristof , Saab Marina , Cazin Catherine S. J. , Cavallo Luigi , Nolan Steven P. , Gessner Viktoria H.
Published: July 2021

Secondary ligand–metal interactions are decisive in many catalytic transformations. While arene–gold interactions have repeatedly been reported as critical structural feature in many high‐performance gold catalysts, we herein report that these interactions can also be replaced by Au⋅⋅⋅H−C hydrogen bonds without suffering any reduction in catalytic performance. Systematic experimental and computational studies on a series of ylide‐substituted phosphines featuring either a PPh3 (PhYPhos) or PCy3 (CyYPhos) moiety showed that the arene‐gold interaction in the aryl‐substituted compounds is efficiently compensated by the formation of Au⋅⋅⋅H−C hydrogen bonds. The strongest interaction is found with the C−H moiety next to the onium center, which due to the polarization results in remarkably strong interactions with the shortest Au⋅⋅⋅H−C hydrogen bonds reported to date. Calorimetric studies on the formation of the gold complexes further confirmed that the PhYPhos and CyYPhos ligands form similarly stable complexes. Consequently, both ligands showed the same catalytic performance in the hydroamination, hydrophenoxylation and hydrocarboxylation of alkynes, thus demonstrating that Au⋅⋅⋅H−C hydrogen bonds are equally suited for the generation of highly effective gold catalysts than gold‐arene interactions. The generality of this observation was confirmed by a comparative study between a biaryl phosphine ligand and its cyclohexyl‐substituted derivative, which again showed identical catalytic performance. These observations clearly support Au⋅⋅⋅H−C hydrogen bonds as fundamental secondary interactions in gold catalysts, thus further increasing the number of design elements that can be used for future catalyst construction.
Continuous flow hydrogenation with Pd complexes of pyridine‐benzotriazole ligands
Authors: Yılmaz Filiz , Hür Deniz
Published: July 2021

The use of continuous flow systems in chemical synthesis provides great advantages in terms of sustainability, efficiency, and safety. The ability to control reaction parameters such as temperature, pressure, and catalyst exposure in flow system enables rapid optimization of reaction conditions. In the present study, palladium complexes of 1‐(piridin‐2‐il)‐1H‐benzo[d][1,2,3]triazol, N‐((1H‐benzo[d][1,2,3]triazol‐1‐il)metil)piridin‐2‐amin, and (1H‐benzo[d][1,2,3]triazol‐1‐yl)(pyridin‐2‐yl)methanone ligands were synthesized and characterized. The catalytic activities of complexes are investigated in the hydrogenation of various alkenes such as styrene, cyclohexene, and 1‐octene under continuous flow conditions. The complexes showed very high activity at 10‐bar H2 pressure and 50°C for short periods of 5–10 min. The catalysts reused for 10 cycles with no significant loss of catalytic activity.
Analysis of mechanical, thermal, electrical andEMIshielding properties of graphite/carbon fiber reinforced polypropylene composites prepared via a twin screw extruder
Authors: Kaushal Ashish , Singh Vishal
Published: July 2021

The present research focuses on the preparation of an efficient material that acts as a deterrent to electromagnetic pollution. In this study, graphite and carbon fiber (CF) reinforced polypropylene (PP) composites (GCF) are prepared using a melt processing technique via a twin‐screw extruder. The prepared composites were evaluated for mechanical, thermal, DC conductivity, and EMI shielding properties. There is a rise in the tensile strength (4.32%) and thermal stability (6.57%) of composites were recorded as compared to pure PP. The fractured morphology of the composites showed the breakdown of CF, leading to the improvement in the tensile strength of the composites. An increase in electrical conductivity was seen at maximum (GCF4) filler loading indicating 2.31 × 10−4 S/cm which is much better than the pure PP value (2.07 × 10−10 S/cm). The maximum value of shielding effectiveness is achieved at the maximum weight percentage of filler loading which is −44.43 dB with a thickness of 2 mm covering the X‐band (8.2–12.4 GHz).
Electrospun scaffolds for wound healing applications from poly(4‐hydroxybutyrate): A biobased and biodegradable linear polymer with high elastomeric properties
Authors: Keridou Ina , Franco Lourdes , Martínez Juan C. , Turon Pau , Del Valle Luis J. , Puiggalí Jordi
Published: July 2021

Electrospun scaffolds of the biodegradable and biocompatible poly‐4‐hydroxybutyrate (P4HB) polyester have been prepared using horizontal and vertical set‐up configurations of electrospinning. Specifically, it has been evaluated the influence of solvent, polymer concentration, and processing parameters, such as applied voltage, flow rate, and needle tip‐collector distance. Scaffolds obtained under the most favorable conditions were characterized in terms of crystallinity, lamellar supramolecular order, thermal (including calorimetric and thermogravimetric data), mechanical, and surface properties. Results pointed out significant differences with respect to commercial sutures (based in P4HB, e.g., MonoMax®) and demonstrated that electrospun scaffolds were constituted by crystalline microfibers with a tangled distribution that leads to high modulus Young modulus (4 MPa), maximum strength (28 MPa), and elongation (360%). Furthermore, new scaffolds had thermal stability and a rough surface that led to a hydrophobic character (105°). Scaffolds could also be successfully loaded during the electrospinning process with a peptide analog to the fibroblast growth factor (e.g., CYRSRKYSSWYVALKRC), giving rise to fully biocompatible samples with a clear acceleration in wound healing.
Anti‐Cortactin Autoantibodies Are Associated With Key Clinical Features in Adult Myositis But Are Rarely Present in Juvenile Myositis
Authors: Pinal‐Fernandez Iago , Pak Katherine , Gil‐Vila Albert , Baucells Andres , Plotz Benjamin , Casal‐Dominguez Maria , Derfoul Assia , Martinez‐Carretero Maria Angeles , Selva‐O'Callaghan Albert , Sabbagh Sara , Casciola‐Rosen Livia , Albayda Jemima , Paik Julie , Tiniakou Eleni , Danoff Sonye K. , Lloyd Thomas E. , Miller Frederick W. , Rider Lisa G. , Christopher‐Stine Lisa , Mammen Andrew L. ,   the Childhood Myositis Heterogeneity Collaborative Study Group
Published: July 2021

Objective

To define the prevalence and clinical phenotype of anti‐cortactin autoantibodies in adult and juvenile myositis.

Methods

In this longitudinal cohort study, anti‐cortactin autoantibody titers were assessed by enzyme‐linked immunosorbent assay in 670 adult myositis patients and 343 juvenile myositis patients as well as in 202 adult healthy controls and 90 juvenile healthy controls. The prevalence of anti‐cortactin autoantibodies was compared among groups. Clinical features of patients with and those without anti‐cortactin autoantibodies were also compared.

Results

Anti‐cortactin autoantibodies were more common in adult dermatomyositis (DM) patients (15%; P = 0.005), particularly those with coexisting anti–Mi‐2 autoantibodies (24%; P = 0.03) or anti–NXP‐2 autoantibodies (23%; P = 0.04). In adult myositis, anti‐cortactin was associated with DM skin involvement (62% of patients with anti‐cortactin versus 38% of patients without anti‐cortactin; P = 0.03), dysphagia (36% versus 17%; P = 0.02) and coexisting anti–Ro 52 autoantibodies (47% versus 26%; P = 0.001) or anti‐NT5c1a autoantibodies (59% versus 33%; P = 0.001). Moreover, the titers of anti‐cortactin antibodies were higher in patients with interstitial lung disease (0.15 versus 0.12 arbitrary units; P = 0.03). The prevalence of anti‐cortactin autoantibodies was not different in juvenile myositis patients (2%) or in any juvenile myositis subgroup compared to juvenile healthy controls (4%). Nonetheless, juvenile myositis patients with these autoantibodies had a higher prevalence of “mechanic's hands” (25% versus 7%; P = 0.03), a higher number of hospitalizations (2.9 versus 1.3; P = 0.04), and lower peak creatine kinase values (368 versus 818 IU/liter; P = 0.02) than those without anti‐cortactin.

Conclusion

The prevalence of anti‐cortactin autoantibodies is increased in adult DM patients with coexisting anti–Mi‐2 or anti–NXP‐2 autoantibodies. In adults, anti‐cortactin autoantibodies are associated with dysphagia and interstitial lung disease.
Anatomy education for medical students in the United Kingdom and Republic of Ireland in 2019: A 20‐year follow‐up
Authors: Smith Claire F. , Freeman Samuel K. , Heylings David , Finn Gabrielle M. , Davies D. Ceri
Published: July 2021

Anatomical education in the United Kingdom (UK) and Ireland has long been under scrutiny, especially since the reforms triggered in 1993 by the General Medical Council's “Tomorrow's Doctors.” The aim of the current study was to investigate the state of medical student anatomy education in the UK and Ireland in 2019. In all, 39 medical schools completed the survey (100% response rate) and trained 10,093 medical students per year cohort. The teachers comprised 760 individuals, of these 143 were employed on full‐time teaching contracts and 103 were employed on education and research contracts. Since a previous survey in 1999, the number of part‐time staff has increased by 300%, including a significant increase in the number of anatomy demonstrators. In 2019, anatomy was predominantly taught to medical students in either a system‐based or hybrid curriculum. In all, 34 medical schools (87%) used human cadavers to teach anatomy, with a total of 1,363 donors being used per annum. Gross anatomy teaching was integrated with medical imaging in 95% of medical schools, embryology in 81%, living anatomy in 78%, neuroanatomy in 73%, and histology in 68.3%. Throughout their five years of study, medical students are allocated on average 85 h of taught time for gross anatomy, 24 h for neuroanatomy, 24 h for histology, 11 h for living anatomy, and 10 for embryology. In the past 20 years, there has been an average loss of 39 h dedicated to gross anatomy teaching and a reduction in time dedicated to all other anatomy sub‐disciplines.
Copper‐Catalyzed Synthesis of 5‐Aryl‐6‐(Trifluoromethyl)‐2,3‐Dihydropyrazolo[1,2‐a]Pyrazol‐1(5H)‐One
Authors: Zhang Xinyu , Wang Hui , Xie Lili , You Chenhui , Han Xiaoyan , Weng Zhiqiang
Published: July 2021

An efficient protocol for the synthesis of 5‐aryl‐6‐(trifluoromethyl)‐2,3‐dihydropyrazolo[1,2‐a]pyrazol‐1(5H)‐one derivatives through a copper‐catalyzed [3+2]‐cycloaddition of azomethine imines with 3,3,3‐trifluoropropyne (generated in situ from dehydrobromination of 2‐bromo‐3,3,3‐trifluoropropene under base conditions) is developed. The advantages of this transformation are the broad substrate scope and the good functional group compatibility. The subsequent oxidation and nucleophilic substitution/aromatization provide a new approach to 4‐trifluoromethylated pyrazol‐1‐yl propanoic acids.
Heterobimetallic Cluster‐Based Coordination Polymers: Assembly, Structures and Third‐Order Nonlinear Optical Properties
Authors: Cao Chen , Bao Shu‐Jin , Tang Xiao‐Yan , Xu Ze‐Ming , Ni Chun‐Yan , Lang Jian‐Ping
Published: July 2021

Reactions of (NH4)2WS4 with CuCN, CuCN/1,2‐bis(4‐pyridyl)propane (bppa) or [Cu(MeCN)4]PF6/bppa under different reaction conditions afforded a set of two‐ or three‐dimensional W/Cu/S cluster‐based coordination polymers including {[Et4N]2[WS4Cu4(μ‐CN)2(μ‐I)2]}n (1), [WS4Cu4(μ‐CN)2(bppa)2]n (2) and {[WS4Cu4(bppa)4](PF6)2}n (3), respectively. Compound 2 can be readily formed from reaction of 1 with bppa under solvothermal conditions. Compounds 1 and 2 feature two‐dimensional networks with a “sql” topology, while 3 possesses a two‐fold interpenetrated three‐dimensional net with a rare “reo” topology. Compounds 1–3 in DMF exhibited different third‐order nonlinear optical responses, and they all showed a reverse saturable absorption while 2 held a strong self‐focusing effect.
Reduced brain volume and white matter alterations in Shank3‐deficient rats
Authors: Golden Carla E. M. , Wang Victoria X. , Harony‐Nicolas Hala , Hof Patrick R. , Buxbaum Joseph D.
Published: July 2021

Mutations and deletions in the SHANK3 gene cause the major neurodevelopmental features of Phelan–McDermid syndrome (PMS), which is characterized by intellectual disability, autism spectrum disorder, and sensory hyporeactivity. SHANK3 encodes a key structural component of excitatory synapses important for synaptogenesis. Clinical assessments and limited brain imaging studies of patients with PMS have uncovered regional volume reductions and white matter thinning. While these impairments have been replicated ex vivo in pups of a rat model, brain structure has not been assessed in rats in vivo or in adults. We assessed the brain structure of heterozygous and homozygous adult Shank3‐deficient male rats in comparison to wild‐type littermates with magnetic resonance imaging using both anatomical assessments and diffusion tensor imaging (DTI). Shank3‐deficient rats showed a reduction in overall brain size and the absolute volume of the neocortex, piriform cortex, thalamus, forebrain, inferior and superior colliculi, internal capsule, and anterior commissure. The superior colliculus was decreased in relative volume. DTI revealed that axial diffusion and fractional anisotropy were reduced in the external capsule and mean diffusion was increased in the fornix, suggesting that restriction of diffusion perpendicular to the axis of the axonal fibers was impaired in these white matter tracts. Therefore, Shank3‐deficient rats replicate the reduced brain volume and altered white matter phenotypes present in PMS. Our results indicate that the loss of a glutamatergic synaptic protein, Shank3, has structural consequences at the level of the whole brain. The brain regions that were altered represent potential cross‐species structural biomarkers that warrant further study.
Tazarotene‐induced gene 1 interacts with Polo‐like kinase 2 and inhibits cell proliferation in HCT116 colorectal cancer cells
Authors: Wang Chun‐Hua , Lu Tzung‐Ju , Wang Lu‐Kai , Wu Chang‐Chieh , Chen Mao‐Liang , Kuo Chan‐Yen , Shyu Rong‐Yaun , Tsai Fu‐Ming
Published: July 2021

Tazarotene‐induced gene 1 (TIG1) is considered to be a tumor suppressor gene that is highly expressed in normal or well‐differentiated colon tissues, while downregulation of TIG1 expression occurs in poorly differentiated colorectal cancer (CRC) tissues. However, it is still unclear how TIG1 regulates the tumorigenesis of CRC. Polo‐like kinases (Plks) are believed to play an important role in regulating the cell cycle. The performance of PLK2 in CRC is negatively correlated with the differentiation status of CRC tissues. Here, we found that PLK2 can induce the growth of CRC cells and that TIG1 can prevent PLK2 from promoting the proliferation of CRC cells. We also found that the expression of PLK2 in CRC cells was associated with low levels of Fbxw7 protein and increased expression of cyclin E1. When TIG1 was coexpressed with PLK2, the changes in Fbxw7/cyclin E1 levels induced by PLK2 were reversed. In contrast, silencing TIG1 promoted the proliferation of CRC, and when PLK2 was also silenced, the proliferation of CRC cells induced by TIG1 silencing was significantly inhibited. The above research results suggest that TIG1 can regulate the tumorigenesis of CRC by regulating the activity of PLK2.
Enhancing the Separation Efficiency in Acetic Acid Manufacturing by Methanol Carbonylation
Authors: Dimian Alexandre C. , Kiss Anton A.
Published: July 2021

Acetic acid is an essential chemical used in the production of many chemical products. Using methanol as bio‐building block, the acetic acid produced may be incorporated in bio‐based products. This study deals with enhancing the efficiency of separations in a process using a homogeneous catalyst, which is the most applied today industrially. Several configurations for downstream processing by distillation are investigated using effective combinations of fully thermally coupled columns, namely, dividing‐wall columns, alone or combined with heat pumps. The results indicate that the three‐column direct sequence may be effectively replaced by a two‐column sequence. Overall, the total annual cost is reduced by 34 %. The cost of compressor may be paid back in 1.5 years by the saved energy. Low energy intensity is achieved by tight integration with the reaction section.
Static Retention of Dynamic Chiral Arrangements for Achiral Shear Thinning Metal–Organic Colloids
Authors: Huang Jian‐Cai , Xiao Hui , Chen Zhixin , Zheng Wenxu , Huang Chang‐Cang , Wu Shu‐Ting , Xie Zenghong , Zhuang Naifeng
Published: July 2021

Chiral compounds are known to be important not only because they are the fundamental components of living organisms, but also for their unique chiroptical properties. In recent years, scientists have fabricated several chiral organic supramolecular aggregates by using chiral physical fields, such as vortex flow. Herein, the relationship between dynamic chiroptical properties and rheological nature is discussed, suggesting the shear thinning properties of non‐Newtonian fluids might help colloidal particles adopt a chiral arrangement in vortices. Furthermore, the storage modulus of colloids could be increased by adding a linking agent, which successfully kept the dynamic chiroptical properties in the static state. Moreover, the salt effect on the host–guest interaction involved in the colloids was studied, the results suggested a significant enhancement of the transferred dynamic circular dichroism for the achiral guest molecule.
Carbon Dioxide Capture Enhanced by Pre‐Adsorption of Water and Methanol in UiO‐66
Authors: Jajko Gabriela , Kozyra Paweł , Gutiérrez‐Sevillano Juan José , Makowski Wacław , Calero Sofia
Published: July 2021

The rapidly rising level of carbon dioxide in the atmosphere resulting from human activity is one of the greatest environmental problems facing our civilization today. Most technologies are not yet sufficiently developed to move existing infrastructure to cleaner alternatives. Therefore, techniques for capturing carbon dioxide from emission sources may play a key role at the moment. The structure of the UiO‐66 material not only meets the requirement of high stability in contact with water vapor but through the water pre‐adsorbed in the pores, the selectivity of carbon dioxide adsorption is increased. We successfully applied the recently developed methodology for water adsorption modelling. It allowed to elucidate the influence of water on CO2 adsorption and study the mechanism of this effect. We showed that water is adsorbed in octahedral cage and stands for promotor for CO2 adsorption in less favorable space than tetrahedral cages. Water plays a role of a mediator of adsorption, what is a general idea of improving affinity of adsorbate. On the basis of pre‐adsorption of methanol as another polar solvent, we have shown that the adsorption sites play a key role here, and not, as previously thought, only the interaction between the solvent and quadrupole carbon dioxide. Overall, we explained the mechanism of increased CO2 adsorption in the presence of water and methanol, as polar solvents, in the UiO‐66 pores for a potential post‐combustion carbon dioxide capture application.
Vibrational circular dichroism of d‐amino acid‐containing peptide NdWFamide in the crystal form
Authors: Yamagishi Hiroki , Sato Hisako , Kawamura Izuru
Published: July 2021

Microcrystals of l‐Asn‐d‐Trp‐l‐Phe‐NH2 (NdWFamide), a tripeptide derived from Aplysia kurodai that exhibits invertebrate cardiac activity, were evaluated by vibrational circular dichroism (VCD). The chirality of the tryptophan residue at the second position in NdWFamide was associated with the conformation and biological characteristics. The VCD spectrum of NdWFamide was a mirror image of its enantiomer; however, it was significantly different from that of its diastereomer, NWFamide, which is its precursor. The obtained VCD signals of NdWFamide were in good agreement with the VCD signals that were calculated based on the optimized aggregates of NdWFamide, which formed a helical‐like backbone conformation. The evaluation of the VCD results revealed the conformation of NdWFamide in the crystalline state and succeeded in distinguishing its stereoisomers. Therefore, this study demonstrates VCD as a useful method for the structural analysis of naturally occurring d‐amino acid‐containing peptides.
Chemomechanical effects of oxidizer‐CO2 systems upon hydraulically fractured unconventional source rock
Authors: Hull Katherine L. , Abousleiman Younane N.
Published: July 2021

Carbon dioxide (CO2) as supercritical (scCO2) or foamed (CO2‐Foam) fluid has been tested many times as a fracturing fluid, though it has not yet proven viable. Many challenges have been identified with scCO2 as a fracturing fluid, including poor additive solubility, low viscosity, and limited accessibility. However, CO2 is known to adsorb to organic matter (OM) and displace methane (i.e., enhanced coal bed methane [ECBM] operations), or to mobilize oil as in tertiary enhanced oil recovery. In this study we augment the efficacy of the kerogen control fluid (KCF) for stimulating unconventional rock formations by alternating aqueous oxidizing fracturing fluid with CO2 injection or by combining oxidizers directly with CO2 as a new additive. To this end, KCF‐CO2 tests were designed to treat OM and extend the depth of permeability enhancement. We report the first attempt to combine oxidizer with CO2 in the presence of source shale rocks at elevated temperature and pressure. Scanning electron microscopy imaging of the treated shale sample surfaces demonstrate potential porosity and permeability enhancement, though some mineral and organic deposits are also observed, which may prove to be detrimental. Meanwhile, alternating water‐based KCF with CO2 provides a potential improvement to the KCF as predicted by early lab results on OM. The KCF‐CO2 concept has no equivalent to date in unconventional hydraulic fracturing operations. This technology will contribute to reducing the footprint of anthropogenic CO2 and enhancing its permanent sequestration in unconventional stimulated reservoirs, compliant with our global clean energy initiative of carbon capture, utilization, and storage.
Effects of control temperature, ablation time, and background tissue in radiofrequency ablation of osteoid osteoma: A computer modeling study
Authors: Rivas Ricardo , Hijlkema Rudy B. , Cornelissen Ludo J. , Kwee Thomas C. , Jutte Paul C. , van Ooijen Peter M. A.
Published: July 2021

To study the effects of the control temperature, ablation time, and the background tissue surrounding the tumor on the size of the ablation zone on radiofrequency ablation (RFA) of osteoid osteoma (OO). Finite element models of non‐cooled temperature‐controlled RFA of typical OOs were developed to determine the resulting ablation radius at control temperatures of 70, 80, and 90°C. Three different geometries were used, mimicking common cases of OO. The ablation radius was obtained by using the Arrhenius equation to determine cell viability. Ablation radii were larger for higher temperatures and also increased with time. All geometries and control temperatures tested had ablation radii larger than the tumor. The ablation radius developed rapidly in the first few minutes for all geometries and control temperatures tested, developing slowly towards the end of the ablation. Resistive heating and the temperature distribution showed differences depending on background tissue properties, resulting in differences in the ablation radius on each geometry. The ablation radius has a clear dependency not only on the properties of the tumor but also on the background tissue. Lower background tissue's electrical conductivity and blood perfusion rates seem to result in larger ablation zones. The differences observed between the different geometries suggest the need for patient‐specific planning, as the anatomical variations could cause significantly different outcomes where models like the one here presented could help to guarantee safe and successful tumor ablations.
Monolayer 1T and 1T′ MoSO as Promising Electrocatalyst for Hydrogen Evolution based on First Principle Calculations
Authors: Li Fei‐Fei , Niu Zi‐Ping , Zhang Li‐Xin
Published: July 2021

Molybdenum disulfide (MoS2) has been regarded as one of the most promising candidates for replacing Pt group noble metals as an efficient electrocatalyst to enhance the hydrogen evolution reaction (HER) in consideration of its relatively high earth abundance. Recent studies show that the catalytic efficiency of MoS2 for HER can be promoted by the presence of 1T‐phase MoS2. It is hard to precisely control the formation of 1T‐MoS2, however, due to its metastability relative to 2H‐MoS2. Elevating the stability of 1T phase allotrope is therefore of great importance and could be realized by replacing divalent S with monovalent elements or groups according to crystal field theory, which has been demonstrated through our first‐principles density functional theory (DFT) calculation results. Differential Gibbs free energy analysis for hydrogen adsorption (ΔGH*) suggest that 1T and 1T′ MoSO (O doped MoS2) might be taken as potential candidate catalysts for HER process with better performance than 1T and 1T′ MoS2. We also propose a probable approach to synthesize 1T and 1T′ MoSO under oxidation circumstance environment of graphene oxide.
Structural, Thermal, and Electronic Properties of Two‐Dimensional Gallium Oxide (β‐Ga2O3) from First‐Principles Design
Authors: Anam Bushra , Gaston Nicola
Published: July 2021

Two‐dimensional (2D) materials with exotic electronic, optical and mechanical properties have attracted tremendous attention in the last two decades, due to their potential applications in electronics, energy storage and conversion technologies. However, only a few dozen 2D materials have been successfully synthesized or exfoliated. Motivated by the recent discovery of 2D gallenene, we have explored new 2D allotropes of β‐Ga2O3, an emerging wide‐band gap transparent conductive oxide (TCO) with a wide range of semiconducting applications. All the possible 2D allotropes of β‐Ga2O3 with high energetic stability have been predicted using particle swarm optimization, combined with density functional theory calculations. The structural and dynamical stability of the predicted 2D allotropes has been analyzed. Although β‐Ga2O3 is not a van der Waals material, results predict that one or two allotropes of β‐Ga2O3 are stable. In addition, the accurate band structures of these 2D semiconducting oxides have been calculated using both the GGA and LDA‐1/2 approach. Remarkably, monolayer Ga2O3(100) has a larger indirect band gap of 4 eV, demonstrating a new avenue for the discovery of 2D β‐Ga2O3 based nano‐devices with enhanced electronic properties.
DrugWAS: Drug‐wide Association Studies for COVID‐19 Drug Repurposing
Authors: Bejan Cosmin A. , Cahill Katherine N. , Staso Patrick J. , Choi Leena , Peterson Josh F. , Phillips Elizabeth J.
Published: July 2021

This study aimed to systematically investigate if any of the available drugs in the electronic health record (EHR) can be repurposed as potential treatment for coronavirus disease 2019 (COVID‐19). Based on a retrospective cohort analysis of EHR data, drug‐wide association studies (DrugWAS) were performed on 9,748 patients with COVID‐19 at Vanderbilt University Medical Center (VUMC). For each drug study, multivariable logistic regression with overlap weighting using propensity score was applied to estimate the effect of drug exposure on COVID‐19 disease outcomes. Patient exposure to a drug between 3‐months prior to the pandemic and the COVID‐19 diagnosis was chosen as the exposure of interest. All‐cause of death was selected as the primary outcome. Hospitalization, admission to the intensive care unit, and need for mechanical ventilation were identified as secondary outcomes. Overall, 17 drugs were significantly associated with decreased COVID‐19 severity. Previous exposure to two types of 13‐valent pneumococcal conjugate vaccines, PCV13 (odds ratio (OR), 0.31, 95% confidence interval (CI), 0.12–0.81 and OR, 0.33, 95% CI, 0.15–0.73), diphtheria toxoid and tetanus toxoid vaccine (OR, 0.38, 95% CI, 0.15–0.93) were significantly associated with a decreased risk of death (primary outcome). Secondary analyses identified several other significant associations showing lower risk for COVID‐19 outcomes: acellular pertussis vaccine, 23‐valent pneumococcal polysaccharide vaccine (PPSV23), flaxseed extract, ethinyl estradiol, estradiol, turmeric extract, ubidecarenone, azelastine, pseudoephedrine, dextromethorphan, omega‐3 fatty acids, fluticasone, and ibuprofen. In conclusion, this cohort study leveraged EHR data to identify a list of drugs that could be repurposed to improve COVID‐19 outcomes. Further randomized clinical trials are needed to investigate the efficacy of the proposed drugs.
Tissue N‐Glycan Analysis Using LC‐MS, MS/MS, and MSn
Authors: Suzuki Noriko
Published: July 2021

Tissue glycans usually contain various structures, from simple to highly complicated, in different quantities. N‐Glycans are particularly heterogeneous, with up to pentaantennary structures, different branch sequences, and several isomeric structures. 2‐Aminopyridine (PA) tagging on released N‐glycans is useful for separating isomers and to quantitatively analyze both the major and minor glycan structures in tissues using reversed‐phase liquid chromatography (LC)−mass spectrometry (MS) and MS/MS analysis. Because the structural differences of PA‐N‐glycans influence their retention on a reversed‐phase C18 column, it is easy to deduce the core structure, including core Fuc and bisecting GlcNAc as well as the branching pattern of each PA‐N‐glycan, based on the results of elution position, full MS, and MS/MS analysis. If more detailed structural analysis is required, combining sequential exoglycosidase digestions, sialic acid linkage−specific alkylamidation (SALSA), and/or SALSA/permethylation is useful for determining glycosidic linkages of branches. This article includes detailed protocols for the preparation of N‐glycans released from glycoproteins/glycopeptides by glycoamidase F or hydrazinolysis, PA‐tagging of N‐glycans, fractionation with anion‐exchange chromatography, and chemical or enzymatic modifications of PA‐N‐glycans, as well as reversed‐phase LC‐MS, MS/MS, and MSn analysis of PA‐N‐glycans from tissues. © 2021 Wiley Periodicals LLC.

Basic Protocol 1: Preparation of released N‐glycans from tissue samples using glycoamidase F

Alternate Protocol: Preparation of released N‐glycans from tissue samples by hydrazinolysis

Basic Protocol 2: PA‐tagging of N‐glycans and sample cleanup

Support Protocol 1: Monitoring of PA‐N‐glycans using normal‐phase HPLC

Basic Protocol 3: Anion‐exchange chromatography of PA‐N‐glycans

Basic Protocol 4: Sequential exoglycosidase digestions

Basic Protocol 5: Determination of Sia‐linkages by SALSA

Support Protocol 2: Cotton‐HILIC solid‐phase extraction to remove reagents for alkylamidation

Basic Protocol 6: Sequential modifications of glycans with SALSA and permethylation

Basic Protocol 7: LC‐MS and MS/MS analysis of PA‐N‐glycans (before permethylation)

Basic Protocol 8: LC‐MS, MS/MS, and MSn analysis of PA‐N‐glycans (after permethylation)
Models of Inflammation: Carrageenan‐ or Complete Freund's Adjuvant (CFA)–Induced Edema and Hypersensitivity in the Rat
Authors: McCarson Kenneth E. , Fehrenbacher Jill C.
Published: July 2021

Animal models of inflammation are used to assess the production of inflammatory mediators at sites of inflammation, the processing of pain sensation at CNS sites, the anti‐inflammatory properties of agents such as nonsteroidal anti‐inflammatory drugs (NSAIDs), and the efficacy of putative analgesic compounds in reversing cutaneous hypersensitivity. Detailed in this article are methods to elicit and measure carrageenan‐ and complete Freund's adjuvant (CFA)–induced cutaneous inflammation. Due to possible differences between the dorsal root sensory system and the trigeminal sensory system, injections into either the footpad or vibrissal pad are described. In this manner, cutaneous inflammation can be assessed in tissue innervated by the lumbar dorsal root ganglion neurons (footpad) or by the trigeminal ganglion neurons (vibrissal pad). © 2021 Wiley Periodicals LLC.
Black Scoter habitat use along the southeastern coast of the United States
Authors: Plumpton Hannah M. , Silverman Emily D. , Ross Beth E.
Published: July 2021

While the Atlantic Coast of the United States and Canada is a major wintering area for sea ducks, knowledge about their wintering habitat use is relatively limited. Black Scoters have a broad wintering distribution and are the only open water species of sea duck that is abundant along the southeastern coast of the United States. Our study identified variables that affected Black Scoter (Melanitta americana) distribution and abundance in the Atlantic Ocean along the southeastern coast of the United States. We used aerial survey data from 2009 to 2012 provided by the United States Fish and Wildlife Service to identify variables that influenced Black Scoter distribution. We used indicator variable selection to evaluate relationships between Black Scoter habitat use and a variety of broad‐ and fine‐scale oceanographic and weather variables. Average time between waves, ocean floor slope, and the interaction of bathymetry and distance to shore had the strongest association with southeastern Black Scoter distribution.
Pro‐environmental behavior: Social norms, intrinsic motivation and external conditions
Authors: Silvi Mariateresa , Padilla Emilio
Published: July 2021

Pro‐environmental behaviors (PEBs) have been linked in the literature to social norms, intrinsic motivation and external conditions. However, no study has jointly analyzed these factors on a cross‐country dataset and given a holistic explanation of the variance observed in the adoption rates of PEBs across countries. Using a dataset measuring individual adoption of eight PEBs in the European Union's 28 member states (in 2018), we econometrically test these three groups of factors on a wider scale. We assess the importance of intrinsic motivation as a dominant factor and show how differing levels of intrinsic motivation influence the effectiveness of external conditions, such as monetary incentives and green infrastructures. The results suggest that two‐pronged policies, which take into account intrinsic motivation and external conditions, are needed to reach a high observance rate in the population in the short and in the long term. The wider significance of these results for policy is discussed.
Flexible Synthesis and Herbicidal Activity of Fully Substituted 3‐Hydroxypyrazoles
Authors: Judge Neil R. , Chacktas Géraud , Ma Ling , Schink Anke , Buckpesch Rainer , Schmutzler Dirk , Machettira Anu B. , Dietrich Hansjörg , Asmus Elisabeth , Bierer Donald , McLeod Michael C.
Published: July 2021

The synthesis and herbicidal efficacy of a novel library of fully substituted 3‐hydroxypyrazoles is reported. An efficient, divergent approach to introduce phenyl, phenoxy, phenylsulfanyl, anilino and benzyl substituents in the 4‐position of the pyrazole, alongside a flexible synthesis of N1‐alkyl analogues is described via final step diversification of key intermediates. Herbicidal screening of the prepared compounds against key weed species identified the lead compound 2‐[4‐(2,4‐difluorophenoxy)‐1,5‐dimethyl‐pyrazol‐3‐yl]oxy‐5‐fluoropyrimidine, which was prepared on a multi‐gram scale using an optimised synthetic route.
Helically Chiral NHC‐Gold(I) Complexes: Synthesis, Chiroptical Properties and Electronic Features of the [5]Helicene‐Imidazolylidene Ligand
Authors: Gauthier Etienne S. , Cordier Marie , Dorcet Vincent , Vanthuyne Nicolas , Favereau Ludovic , Williams J. A. Gareth , Crassous Jeanne
Published: July 2021

We describe the preparation of helically chiral gold(I) complexes bearing a [5]helicenic‐N‐heterocyclic carbene ligand. They were successfully obtained as enantiopure compounds by semi‐preparative chiral HPLC and their structural, chiroptical, and photophysical properties were subsequently investigated. Notably, strong electronic circular dichroism, dual emission from singlet and triplet states, with the timescale of the latter up to the millisecond range at room temperature, and moderate circularly phosphorescence were observed. The σ‐donating and π‐accepting properties of the constituent helical ortho‐fused π‐conjugated carbene were investigated by classical quantitative analysis of the IR stretching frequencies and NMR characteristics of the corresponding Ir(CO)2Cl complex and selenourea.
Isopyrazole‐Masked Tetraketone: Tautomerism and Functionalization for Fluorescent Metal Ligands
Authors: Shirakura Hayato , Manabe Yumehiro , Kasai Chika , Inaba Yuya , Tsurui Makoto , Kitagawa Yuichi , Hasegawa Yasuchika , Yoneda Tomoki , Ide Yuki , Inokuma Yasuhide
Published: July 2021

An isopyrazole (4H‐pyrazole)‐embedded nonane‐2,4,6,8‐tetraone derivative was synthesized as a masked‐tetraketone for stepwise and multiple functionalization. The masked‐tetraketone has six possible tautomers, but exists predominantly as a 12π‐electron conjugated keto‐enamine‐imine‐enol form, which was also observed in the solid state by single crystal X‐ray analysis. Stepwise functionalization to introduce metal‐coordination and fluorescence‐enhancement sites into the masked tetraketone furnished a fluorescent chromophore that indicates metal coordination on a microgram scale by considerably changing the solid‐state emission.
Fluorine‐Labelled Spiro[3.3]heptane‐Derived Building Blocks: Is Single Fluorine the Best?
Authors: Malashchuk Andrii , Chernykh Anton V. , Dobrydnev Alexey V. , Grygorenko Oleksandr O.
Published: July 2021

A reliable methodology for constructing 6‐fluoro‐spiro[3.3]heptane scaffold is developed. A vast library of 2‐mono‐ and 2,2‐difunctionalized 6‐fluoro‐spiro[3.3]heptane‐derived building blocks were obtained in a multigram scale (up to 302 g) though the convergent synthetic strategy. This class of compounds was designed for medicinal chemistry as fluorine‐labelled conformationally restricted isosteres of cyclohexane framework. The structure was confirmed by X‐ray diffraction study, and the physico‐chemical properties (acidity, lipophilicity and water solubility) were characterized. Finally, the generation of virtual compound libraries using the LLAMA software showed that the monofluorinated spiro[3.3]heptane‐derived building blocks demonstrated the highest propensity to populate the lead‐like chemical space as compared to non‐ and difluorinated counterparts, as well as cyclohexane derivatives, while retaining similar three‐dimensionality features.
Recent Advances in Plasmonic Nanostructures Applied for Label‐free Single‐cell Analysis
Authors: Liao Xue‐Wei , Xu Qiu‐Yang , Tan Zheng , Liu Yang , Wang Chen
Published: July 2021

Cellular heterogeneity presents a major challenge in understanding the relationship between cells of particular genotype and response in disease. In order to characterize the cell‐to‐cell differences during the biochemical processes, single‐cell analysis is necessary. Profiting from the unique localized surface plasmon resonance (LSPR) and Mie scattering, plasmonic nanostructures have revealed stable and adjustable scattering signals, avoiding photobleaching, blinking and autofluorescence phenomenon. These characterizations are propitious to the dynamic trace and biological image of single living cells. In this review, we discuss the recent advances in plasmonic nanostructures applied for label‐free detection and monitoring of target cells at single‐cell level by using three different techniques, surface‐enhanced Raman scattering (SERS), surface‐enhanced Infrared absorption spectroscopy (SEIRAS), and dark‐field microscopy. Various avenues to design plasmonic probes combining spectra and imaging for single‐cell analysis are demonstrated as well. We hope this review can highlight the superiority of plasmonic nanostructures in single cellular analysis, and further motivate the development of label‐free cell analysis technique to elucidate cellular diversity and heterogeneity.
Interactive Metal Mixture Toxicity to Daphnia magna Populations as an Emergent Property in a Dynamic Energy Budget Individual-Based Model
Authors: Hansul Simon , Fettweis Andreas , Smolders Erik , De Schamphelaere Karel
Published: July 2021

Environmental risk assessment of metal mixtures is challenging due to the large number of possible mixtures and interactions. Mixture toxicity data cannot realistically be generated for all relevant scenarios. Therefore, methods for prediction of mixture toxicity from single-metal toxicity data are needed. We tested how well toxicity of Cu-Ni-Zn mixtures to Daphnia magna populations can be predicted based on the Dynamic Energy Budget theory with an individual-based model (DEB-IBM), assuming non-interactivity of metals on the physiological level. We exposed D. magna populations to Cu, Ni, and Zn and their mixture at a fixed concentration ratio. We calibrated the DEB-IBM with single-metal data and generated blind predictions of mixture toxicity (population size over time), with account for uncertainty. We compared the predictive performance of the DEB-IBM with respect to mixture effects on population density and population growth rates with that of two reference models applied on the population level, independent action and concentration addition. Our inferred physiological modes of action (pMoA) differed from literature-reported pMoAs, raising the question of whether this is a result of different model selection approaches, intraspecific variability, or whether different pMoAs might actually drive toxicity in a population context. Observed mixture effects were concentration- and endpoint-dependent. The independent action was overall more accurate than the concentration addition but concentration addition-predicted effects on population growth rate were slightly better. The DEB-IBM most accurately predicted effects on 6-week density, including antagonistic effects at high concentrations, which emerged from non-interactivity at the physiological level. Mixture effects on initial population growth rate appear to be more difficult to predict. To explain why model accuracy is endpoint-dependent, relationships between individual-level and population-level endpoints should be illuminated. Environ Toxicol Chem 2021;40:3034–3048. © 2021 SETAC