bluuebunny/crossref_metadata_2025 huggingface dataset:
Stochastic Estimations of the Total Number of Classes for a Clustering having Extremely Large Samples to be Included in the Clustering Engine
Authors: Utimula Keishu , Prayogo Genki I. , Nakano Kousuke , Hongo Kenta , Maezono Ryo
Published: March 2021

Numerous reports have elucidated the classification of a large amount of data using various clustering techniques. However, an increase in data size hinders the applicability of these methods. Here, it is investigated how to deal with the exploding number of possibilities to be sorted into irreducible classes by using a clustering technique when its input capacity cannot accommodate the total number of possibilities. This can be exemplified by atomic substitutions in the supercell modeling of alloys. The number of possibilities is sometimes equal to trillions, which is extremely large to be accommodated in a cluster. Thus, it is not practically feasible to identify directly how many irreducible classes exist even though several techniques are available to perform the clustering. In this regard, a stochastic framework is developed to avoid the shortage limitations, providing a method to estimate the total number of irreducible classes (the order of classes), as a statistical estimate. The main conclusion is that the statistical variation of the number of classes, at each sampling trial, can serve as a promising measure to estimate the total number of irreducible classes. Characteristics of this approach is also discussed by comparing with the conventional one based on Polya's theorem.
From Micromagnetic to In Silico Modeling of Magnetic Nanodisks for Hyperthermia Applications
Authors: Manzin Alessandra , Ferrero Riccardo , Vicentini Marta
Published: March 2021

Magnetic nanodisks have been recently proposed as biomedical tools for therapeutics at the nanoscale level, with a special focus on hyperthermia for cancer cure. Here we present a detailed study of permalloy nanodisks to be used in alternative to superparamagnetic iron oxide nanoparticles, as efficient heating agents that release heat via magnetic hysteresis. A micromagnetic modeling analysis is carried out to identify sizes and ac field parameters that maximize the specific loss power (SLP), guaranteeing the fulfillment of biophysical constraints (Hergt–Dutz limit) and vortex state at remanence (reduced agglomeration effects). The highest SLP (790 W g−1) is found for 100 nm diameter and 20 nm thickness nanodisks, excited at a frequency of 75 kHz. Further analysis elucidates the influence of magnetostatic interactions and local nanodisk‐field orientation on the SLP of nanodisk clusters, which originate from the deposition in target tissues. At high concentrations, magnetostatic interactions can lead to a reduction of 40–50% in the hysteresis losses. From thermal simulations, we finally demonstrate that in a murine model temperature increments comparable to that obtained in calorimetric measurements under quasi‐adiabatic conditions can be achieved only by using an order of magnitude larger dosage of nanodisks, due to blood perfusion effects.
Patterned Blade Coating Strategy Enables the Enhanced Device Reproducibility and Optimized Morphology of Organic Solar Cells
Authors: Yuan Jian , Liu Dongjie , Zhao Heng , Lin Baojun , Zhou Xiaobo , Naveed Hafiz Bilal , Zhao Chao , Zhou Ke , Tang Zheng , Chen Fei , Ma Wei
Published: March 2021

Morphology evolution kinetics at multi‐scale regime is a challenging problem which is critical for industrial fabrication of high‐performance organic solar cells (OSCs). An innovative strategy utilizing a patterned blade to print non‐fullerene (NF) based devices in ambient conditions is demonstrated. A specially designed patterned blade with micro‐cylinder arrays exhibit a reasonable control over the fluid flow at high extensional and shear strain rate to enhance lateral mass transport during blade‐coating. Comparison of patterned and normal blade in printing polymer:NF blend film at different speeds reveals interesting avenues to optimize the blend films morphology. Patterned blade printed PM6:Y6 films yield a PCE of 15.93% as compared to 14.55% from a normal blade. Through in situ and ex situ morphology characterization techniques, the use of patterned blades induce conformational changes in PM6 chains, enabling Y6 to crystallize faster and more efficiently. Such improved blend morphology enables favorable charge transfer and transport to realize superior device performance. A lower stick‐slip effect at the macro‐scale with the patterned blade results in a smoother film promoting device reproducibility. Applications in efficient large‐scale devices, confirming the choice of patterned blade design are reported. The efforts collaborating device engineering, morphology evolution kinetics would enable reproducibility and eased commercialization of OSCs at large scale.
New Cysteine Covalent Modification Strategies Enable Advancement of Proteome‐wide Selectivity of Kinase Modulators
Authors: Guan Ivy , Williams Kayla , Pan Jolyn , Liu Xuyu
Published: March 2021

There has been tremendous progress in covalent inhibitors as evidenced by the ascent of innovative electrophilic warheads with suppressed non‐specific reactivity but enhanced capacity for proximity‐driven covalent reactions with nucleophilic residues in the targeted site. Kinases, a central player in cancers, autoimmune disorders and chronic diseases, represent a highly targeted class of enzymes by covalent inhibitors. However, innovative strategies to afford high selectivity in target recognition remain a pressing need. This minireview focuses on four promising strategies to achieve superior target selectivity through rational design of the covalent engagement. Special emphasis is placed on examples where the selectivity had arisen by complementing the reactivity of protein cysteines with electrophilic warheads specified for distinct covalent chemistry, or inspired from native electrophile signalling in cells.
Iron‐Catalyzed Water Oxidation: O–O Bond Formation via Intramolecular Oxo–Oxo Interaction
Authors: Zhang Hong‐Tao , Su Xiao‐Jun , Xie Fei , Liao Rong‐Zhen , Zhang Ming‐Tian
Published: March 2021

Herein, we report the importance of structure regulation on the O−O bond formation process in binuclear iron catalysts. Three complexes, [Fe2(μ‐O)(OH2)2(TPA)2]4+(1), [Fe2(μ‐O)(OH2)2(6‐HPA)]4+(2) and [Fe2(μ‐O)(OH2)2(BPMAN)]4+(3), have been designed as electrocatalysts for water oxidation in 0.1 M NaHCO3solution (pH 8.4). We found that1and2are molecular catalysts and that O−O bond formation proceeds via oxo–oxo coupling rather than by the water nucleophilic attack (WNA) pathway. In contrast, complex3displays negligible catalytic activity. DFT calculations suggested that theantitosynisomerization of the two high‐valent Fe=O moieties in these catalysts takes place via the axial rotation of one Fe=O unit around the Fe‐O‐Fe center. This is followed by the O−O bond formation via an oxo–oxo coupling pathway at the FeIVFeIVstate or via oxo–oxyl coupling pathway at the FeIVFeVstate. Importantly, the rigid BPMAN ligand in complex3limits theantitosynisomerization and axial rotation of the Fe=O moiety, which accounts for the negligible catalytic activity.
Vapochromism and Magnetochemical Switching of a Nickel(II) Paddlewheel Complex by Reversible NH3 Uptake and Release
Authors: Fürpaß Katharina M. , Peschel Lydia M. , Schachner Jörg A. , Borisov Sergey M. , Krenn Heinz , Belaj Ferdinand , Mösch‐Zanetti Nadia C.
Published: March 2021

Reaction of [NiCl2(PnH)4] (1) (PnH=6‐tert‐butyl‐pyridazine‐3‐thione) with NiCl2 affords the binuclear paddlewheel (PW) complex [Ni2(Pn)4] (2). Diamagnetic complex 2 is the first example of a PW complex capable of reversibly binding and releasing NH3. The NH3 ligand in [Ni2(Pn)4(NH3)] (2⋅NH3) enforces major spectroscopic and magnetic susceptibility changes, thus displaying vapochromic properties (λmax(2)=532 nm, λmax(2⋅NH3)=518 nm) and magnetochemical switching (2: S=0; 2⋅NH3: S=1). Upon repeated adsorption/desorption cycles of NH3 the PW core remains intact. Compound 2 can be embedded into thin polyurethane films (2P) under retention of its sensing abilities. Therefore, 2 qualifies as reversible optical probe for ammonia. The magnetochemical switching of 2 and 2⋅NH3 was studied in detail by SQUID measurements showing that in 2⋅NH3, solely the Ni atom coordinated the NH3 molecule is responsible for the paramagnetic behavior.
The Interrelated Effect of Cations and Electrolyte pH on the Hydrogen Evolution Reaction on Gold Electrodes in Alkaline Media
Authors: Goyal Akansha , Koper Marc T. M.
Published: March 2021

In this work we study the role of alkali metal cation concentration and electrolyte pH in altering the kinetics of the hydrogen evolution reaction (HER) at gold (Au) electrodes. We show that at moderately alkaline pH (pH 11), increasing the cation concentration significantly enhances the HER activity on Au electrodes (with a reaction order ≈0.5). Based on these results we suggest that cations play a central role in stabilizing the transition state of the rate‐determining Volmer step by favorably interacting with the dissociating water molecule (*H–OHδ−–cat+). Moreover, we show that increasing electrolyte pH (pH 10 to pH 13) tunes the local field strength, which in turn indirectly enhances the activity of HER by tuning the near‐surface cation concentration. Interestingly, a too high near‐surface cation concentration (at high pH and high cation concentration) leads to a lowering of the HER activity, which we ascribe to a blockage of the surface by near‐surface cations.
Reduction of the environmental footprint of thermo‐alkali pretreatment by reusing black liquor during anaerobic digestion of lignocellulosic biomasses
Authors: Peyrelasse Christine , Kaparaju Prasad , Lallement Audrey , Marques Melissa , Monlau Florian
Published: March 2021

In this study, the effect of thermo‐alkaline pretreatment and recycling of the liquid fraction (black liquor) for successive pretreatment steps on chemical composition and methane yields from horse manure was investigated. At first, horse manure was subjected to alkaline pretreatment at 70 °C for 1 h (8.6 g NaOH/100 g total solids). Pretreated biomass was then separated into solid and liquid fractions (black liquor). In the subsequent stages, black liquor was mixed with 20% (v/v) of fresh NaOH and was reused to pretreat subsequent batches of horse manure (cycles 1–4). Chemical analyses showed that thermo‐alkaline pretreatment was effective in the delignification and solubilization of organic matter and thereby increased the holocellulose (cellulose and hemicelluloses) content in the solid fraction of horse manure. On comparison with untreated horse manure methane yields (225 ± 1 L CH4 kg−1 VSadded), thermo‐alkaline pretreatment improved the methane yields of horse manure by 39% (313 ± 16 L CH4 kg−1 VSadded). However, the effectiveness of black liquor recycling on methane production decreased (from 39 to 12%) with an increase in the number of recycling steps (from 1 to 4). Nevertheless, recycling of black liquor reduced the consumption of NaOH (40%) and water use (60%). Thus, thermo‐alkaline pretreatment with liquor recycling was found to be an effective pretreatment with an economic gain of 2.4 to 10.4 compared to pretreatment without recycling. © 2021 Society of Chemical Industry and John Wiley & Sons, Ltd
Silk fibroin and ceramic scaffolds: Comparative in vitro studies for bone regeneration
Authors: Deshpande Rucha , Shukla Swati , Sayyad Raeesa , Salunke Shalmali , Nisal Anuya , Venugopalan Premnath
Published: March 2021

Synthetic bone void fillers based on calcium ceramics are used to fill cavities in the bone and promote bone regeneration. More recently, silk fibroin (SF), a protein polymer obtained from Bombyx mori silkworm, has emerged as a promising material in bone void filling. In this work, we have compared the safety and efficacy of two types of silk fibroin‐based bone void fillers with currently used and commercially available ceramic bone void fillers (based on calcium sulphate, beta tricalcium phosphate, and beta tricalcium phosphate with hydroxyapatite). Further, we have also evaluated these two types of SF scaffolds, which have strikingly different structural attributes. The biocompatibility of these scaffolds was comparable as assessed by cytotoxicity assay, cellular adhesion assay, and immunogenic assay. Ability of the scaffolds to support differentiation of human mesenchymal stem cells (hMSCs) into an osteoblastic lineage was also evaluated in an in vitro differentiation experiment using reverse transcriptase polymerase chain reaction analysis. These results revealed that cells cultured on SF scaffolds exhibit higher expression of early to late markers such as Runx2, BMPs, collagen, osterix, osteopontin, and osteocalcin as compared with ceramic‐based scaffolds. This observation was further validated by studying the expression of alkaline phosphatase and calcium deposition. We also show that scaffolds made from same material of SF, but characterized by very different pore architectures, have diverse outcome in stem cell differentiation.
Corticosteroid therapy for 2019‐nCoV‐infected patients: A case series of eight mechanically ventilated patients
Authors: AL‐Rasheedi Mabrouk , Alhazmi Yasir , Almaqwashi Nouf , Mateq Ali Alreshidi , Kardam Abdulaziz , Sharaf Mohammod , Haider Khawaja Husnain
Published: March 2021

High‐dose short‐term corticosteroid therapy is effective and produces favorable clinical outcome in patients with severe 2019‐nCoV infection who are candidates for mechanical ventilation with close monitor/ing for the adverse effect of corticosteroids.
Site‐specifically Incorporated Non‐Canonical Amino Acids into Pseudomonas alcaligenes Lipase to Hydrolyze L‐menthol Propionate among the Eight Isomers
Authors: Yu Zhonglang , Yu Haoran , Tang Haibin , Wang Zhe , Wu Jianping , Yang Lirong , Xu Gang
Published: March 2021

It remains a challenge to improve the diastereopreference of enzymes when there are multiple chiral centers in the substrate, mainly because the limited understanding of mechanism determining diastereoselectivity. Compared with natural amino acids, non‐canonical amino acids (ncAAs) provide side chains with wider range of functional groups and genetically encoded ncAAs have been applied in probing the complex enzyme mechanisms, improving catalytic activity, and even designing enzymes with new catalytic mechanisms. Here, the ncAAs were site‐specifically incorporated into a lipase (PaL) produced by Pseudomonas alcaligenes to explore its diastereopreference mechanism. Menthol propionate has three chiral centers, eight isomers in total. Molecular dynamics (MD) simulations were first applied to analyze the interactions between the active sites of PaL and the target substrate L‐menthol propionate. Furthermore, the four ncAAs (o‐bromophenylalanine, o‐chlorophenylalanine, p‐cyanophenylalanine and p‐aminophenylalanine) were substituted for 9 amino acids sites that potentially influenced three chiral centers and several variants with significant improvement in the diastereopreference were obtained. The diastereomer selectivity of beat variant at Ala253 was 100 % higher than that of the wild‐type. A linear relationship was found between volume, flexibility of the active center and diastereoselectivity.
Stabilization of a 4.7 V High‐Voltage Nickel‐Rich Layered Oxide Cathode for Lithium‐Ion Batteries through Boron‐Based Surface Residual Lithium‐Tuned Interface Modification Engineering
Authors: Wang Wenzhi , Wu Langyuan , Li Zhiwei , Huang Kangsheng , Chen Ziyang , Lv Chen , Dou Hui , Zhang Xiaogang
Published: March 2021

Residual lithium on the surface and the resulting side reactions for high‐energy‐density Ni‐rich layered oxide cathodes principally impede their industrial application and trigger safety concerns. Herein, the successful construction of LiBO2−B2O3 co‐modified single‐crystal LiNi0.6Co0.2Mn0.2O2 (SC‐NCM) as a lithium‐ion battery (LIB) cathode is reported. Boric acid reacts with the surface residual lithium species to form such uniform coating on the SC‐NCM particles, which presents advanced rate and cycling capabilities. As the cathode materials for LIBs, LiBO2−B2O3 co‐modified SC‐NCM delivers a 141.9 mAh g−1 discharge specific capacity at 5 C between 3.0 and 4.5 V versus Li+/Li with 61.4 % capacity retention after 500 cycles, superior to the 20.8 % retention for the pristine SC‐NCM cathode. Besides, the LiBO2‐B2O3 protective layer substantially inhibits the unexpected phase transformation, effectively alleviates the mechanical microcracks, and stabilizes the cathode‐electrolyte interface, even at an extended operational potential window. The proposed microstructure‐modified SC‐NCM cathode provides an affordable and feasible design strategy for Ni‐rich SC‐NCM cathodes towards stable electrochemical performance and prolonged service life at high potential.
5‐Hydroxymethyl‐, 5‐Formyl‐ and 5‐Carboxydeoxycytidines as Oxidative Lesions and Epigenetic Marks
Authors: Schelter Florian , Kirchner Angie , Traube Franziska R. , Müller Markus , Steglich Wolfgang , Carell Thomas
Published: March 2021

The four non‐canonical nucleotides in the human genome 5‐methyl‐, 5‐hydroxymethyl‐, 5‐formyl‐ and 5‐carboxydeoxycytidine (mdC, hmdC, fdC and cadC) form a second layer of epigenetic information that contributes to the regulation of gene expression. Formation of the oxidized nucleotides hmdC, fdC and cadC requires oxidation of mdC by ten‐eleven translocation (Tet) enzymes that require oxygen, Fe(II) and α‐ketoglutarate as cosubstrates. Although these oxidized forms of mdC are widespread in mammalian genomes, experimental evidence for their presence in fungi and plants is ambiguous. This vagueness is caused by the fact that these oxidized mdC derivatives are also formed as oxidative lesions, resulting in unclear basal levels that are likely to have no epigenetic function. Here, we report the xdC levels in the fungus Amanita muscaria in comparison to murine embryonic stem cells (mESCs), HEK cells and induced pluripotent stem cells (iPSCs), to obtain information about the basal levels of hmdC, fdC and cadC as DNA lesions in the genome.
Stable Boron‐Containing Blue‐Photoluminescent Radicals
Authors: Feng Zhongtao , Chong Yuanyuan , Tang Shuxuan , Ruan Huapeng , Fang Yong , Zhao Yue , Jiang Jun , Wang Xinping
Published: March 2021

Main observation and conclusion

It is highly urgent to develop synthetic strategies to make new category of stable luminescent radicals with desired emission wavelength. In this study, we have isolated two dioxoborocyclic radicals (3 and 4) by a direct synthetic route. They were characterized by UV, EPR spectroscopy and SQUID measurements. Their structures were obtained by single‐crystal X‐ray diffraction. Both radicals produce blue‐photoluminescence (458 nm for 3 and 478 nm for 4) by radiative decay from higher excited states (D2/D3) to the ground state (D0) based on theoretical calculation, breaking Kasha rule. The work records a new kind of radical emitters and the first stable radicals with blue emission bands.
Impact of terrorist attacks on social relationships
Authors: Van Overmeire Roel , Van Keer Rose‐Lima , Bilsen Johan
Published: March 2021

Background

People that experience a trauma might also experience problems in their social relationships. However, how witnessing a terrorist attack influences social relationships is still understudied. This is important, as currently, there is more focus on the individual's mental health and not on how this mental health can impact the individual's social relations. In this study, the impact of the experience of a terrorist attack on social relationships was studied.

Methods

In‐depth interviews were conducted, with 31 directly exposed people during the 22 March 2016 attacks in Belgium. Data were analysed using reflexive thematic analysis.

Results

Three factors related to the impact on social relationships were found. First, participants felt that they had changed. This includes feeling more aggressive, guilty, distrusting or psychosomatic factors, such as migraine attacks, which can hamper social visits. Second, the reactions of others on the participant's expressing their feelings and behaviour also caused participants to not feel understood by their social relationships. Third, due the first two factors, participants coped in different ways (e.g. remaining silent and avoiding certain triggers), which in turn caused their social relationships to change.

Conclusions

The social relationships of witnesses of terrorist attacks can be hampered due to both themselves as well as the reaction of others. More awareness seems to be needed on the possible mental health consequences of terrorist attacks for witnesses.
Class II Human Leukocyte Antigen Variants Associate With Risk of Pegaspargase Hypersensitivity
Authors: Liu Yiwei , Yang Wenjian , Smith Colton A. , Cheng Cheng , Karol Seth E. , Larsen Eric C. , Winick Naomi , Carroll William L. , Loh Mignon L. , Raetz Elizabeth A. , Hunger Stephen P. , Winter Stuart S. , Dunsmore Kimberly P. , Devidas Meenakshi , Yang Jun J. , Evans William E. , Jeha Sima , Pui Ching‐Hon , Inaba Hiroto , Relling Mary V.
Published: March 2021

We conducted the first human leukocyte antigen (HLA) allele and genome‐wide association study to identify loci associated with hypersensitivity reactions exclusively to the PEGylated preparation of asparaginase (pegaspargase) in racially diverse cohorts of pediatric leukemia patients: St Jude Children’s Research Hospital’s Total XVI (TXVI, n = 598) and Children’s Oncology Group AALL0232 (n = 2,472) and AALL0434 (n = 1,189). Germline DNA was genotyped using arrays. Genetic variants not genotyped directly were imputed. HLA alleles were imputed using SNP2HLA or inferred using BWAkit. Analyses between genetic variants and hypersensitivity were performed in each cohort first using cohort‐specific covariates and then combined using meta‐analyses. Nongenetic risk factors included fewer intrathecal injections (P = 2.7 × 10−5 in TXVI) and male sex (P = 0.025 in AALL0232). HLA alleles DQB1*02:02, DRB1*07:01, and DQA1*02:01 had the strongest associations with pegaspargase hypersensitivity (P < 5.0 × 10−5) in patients with primarily European ancestry (EA), with the three alleles associating in a single haplotype. The top allele HLA‐DQB1*02:02 was tagged by HLA‐DQB1 rs1694129 in EAs (r2 = 0.96) and less so in non‐EAs. All single nucleotide polymorphisms associated with pegaspargase hypersensitivity reaching genome‐wide significance in EAs were in class II HLA loci, and were partially replicated in non‐EAs, as is true for other HLA associations. The rs9958628 variant, in ARHGAP28 (previously linked to immune response in children) had the strongest genetic association (P = 8.9 × 10−9) in non‐EAs. The HLA‐DQB1*02:02‐DRB1*07:01‐DQA1*02:01 associated with hypersensitivity reactions to pegaspargase is the same haplotype associated with reactions to non‐PEGylated asparaginase, even though the antigens differ between the two preparations.
Missing‐value imputation using the robust singular‐value decomposition: Proposals and numerical evaluation
Authors: García‐Peña Marisol , Arciniegas‐Alarcón Sergio , Krzanowski Wojtek J. , Duarte Diego
Published: March 2021

A common problem in the analysis of data from multi‐environment trials is imbalance caused by missing observations. To get around this problem, Yan proposed a method for imputing the missing values based on the singular‐value decomposition (SVD) of a matrix. However, this SVD can be affected by outliers and produce low quality imputations. In this article, we propose four extensions of the Yan method that are resistant to outliers, replacing the standard SVD method with four robust SVD extensions. We evaluate these methods, using exclusively numerical criteria in a simulation study and in a cross‐validation study based on real data. We conclude that in the presence of outliers, the standard SVD method should not be used; instead, the best alternatives are the robust SVD methods based on sub‐sampling when the percentage of contamination is less than 2% following a completely random missing data mechanism. In any other case, methods that either minimize the L2 norm or that involve L1 regressions are preferable.
Cold plasma treatment improves seed germination and accelerates the establishment of centipedegrass
Authors: Li Ling , Chen Jingbo , Wang Haoran , Guo Hailin , Li Dandan , Li Jianjian , Liu Jianxiu , Shao Hanliang , Zong Junqin
Published: March 2021

Cold plasma seed treatment has the potential for improving seed germination and seedling growth. However, the effects of cold plasma on seed germination and plant growth of perennial plants are unknown. Centipedegrass [Eremochloa ophiuroides (Munro) Hack.] was used to study the effect of cold plasma on seed germination, plant growth, and plant physiological mechanisms. Seeds were treated with different doses (0, 30, 60, 90, 120, 150, 180, and 210 W) of cold plasma. After cold plasma treatment, germination and biophysical characteristics of seeds, turf quality parameters, and physiological responses were investigated. Results showed that 120 W of cold plasma treatment significantly improved germination and turf quality of centipedegrass, and germination rate, germination speed, and uniformity of emergence were improved. Adventitious root numbers and dry weights of shoots and roots of seedlings increased. In addition, water uptake increased because of the increased conductivity and decreased apparent contact angle. Seed reserve utilization parameters, including α‐amylase and protease activities, soluble sugar and protein contents, and seed reserve utilization efficiency, all increased. Mean percentage of turfgrass coverage, stem diameter, leaf thickness, and dry weights of shoots and roots increased. Chlorophyll content, net photosynthetic rate, root activity, and microelements contents also increased. Overall, cold plasma treatment improved the seed germination and turf quality by increasing the water uptake of seeds, seed reserve utilization, photosynthetic efficiency, and nutrient uptake capacity.
Book Reviews
Authors: Buller Jeffrey L.
Published: March 2021

Managing Time and Stress: A Guide for Academic Leaders to Accomplish What Matters
Observational evidence of herbivore‐specific associational effects between neighboring conspecifics in natural, dimorphic populations of Datura wrightii
Authors: Goldberg Jay K. , Sternlieb Sonya R. , Pintel Genevieve , Delph Lynda F.
Published: March 2021

Associational effects—in which the vulnerability of a plant to herbivores is influenced by its neighbors—have been widely implicated in mediating plant–herbivore interactions. Studies of associational effects typically focus on interspecific interactions or pest–crop dynamics. However, associational effects may also be important for species with intraspecific variation in defensive traits. In this study, we observed hundreds of Datura wrightii—which exhibits dimorphism in its trichome phenotype—from over 30 dimorphic populations across California. Our aim was to determine whether a relationship existed between the trichome phenotype of neighboring conspecifics and the likelihood of being damaged by four species of herbivorous insects. We visited plants at three timepoints to assess how these effects vary both within and between growing seasons. We hypothesized that the pattern of associational effects would provide rare morphs (i.e., focal plants that are a different morph than their neighbors) with an advantage in the form of reduced herbivory, thereby contributing to the negative frequency‐dependent selection previously documented in this system. We found the best predictor of herbivory/herbivore presence on focal plants was the phenotype of the focal plant. However, we also found some important neighborhood effects. The total number of plants near a focal individual predicted the likelihood and/or magnitude of herbivory by Tupiochoris notatus, Lema daturaphila, and Manduca sexta. We also found that velvety focal plants with primarily sticky neighbors are more susceptible to infestation by Tupiochoris notatus and Lema daturaphila. This does not align with the hypothesis that associational effects at the near‐neighbor scale contribute to a rare‐morph advantage in this system. Overall, the results of our study show that the number and trichome‐morph composition of neighboring conspecifics impact interactions between D. wrightii and insect herbivores.
Ditopic Hexadentate Ligands with a Central Dihydrobenzo‐diimidazole Unit Forming a [2x2] Zn4 Grid Complex
Authors: Schäfer Bernhard , Suryadevara Nithin , Greisch Jean‐Francois , Fuhr Olaf , Kappes Manfred M. , Ruben Mario
Published: March 2021

A family of ditopic hexadentate ligands based on the parent compound 2,6‐bis(6‐(pyrazol‐1‐yl)pyridin‐2‐yl)‐1,5‐dihydrobenzo[1,2‐d:4,5‐d’]diimidazole (L) was developed and synthesized by using a straightforward condensation reaction, which forms the interlinking central benzo[1,2‐d:4,5‐d’]diimidazole bridge in the ligand backbone. The two secondary amine groups of the benzodiimidazole unit tautomerize and allow the formation of two tauto‐conformers, which upon treatment with metal salts forms different isomeric coordination complexes. Here we report six new derivatives (1–6) that can tautomerize (varying the pyrazolylpyridine part) and 14 derivatives (7–13) with different alkyl and benzyl substitution on secondary amino groups (of L) that prevent the tautomerization. This way, it is possible to study the properties of isomeric coordination complexes and their intrinsic cooperativity by the example of [2x2] grid complexes in the future. A [2x2] Zn4 complex of the ligand L was synthesized and structurally characterized.
Electrochemical Quantitative Evaluation of the Surface Charge of a Poly(1‐Vinylimidazole) Multilayer Film and Application to Nanopore pH Sensor
Authors: Sato Katsuhiko , Sato Fumiya , Kumano Masayuki , Kamijo Toshio , Sato Takaya , Zhou Yuanshu , Korchev Yuri , Fukuma Takeshi , Fujimura Tsutomu , Takahashi Yasufumi
Published: March 2021

Nanopore pH sensing is based on the interaction between the surface charge of the nanopore and ions passing through the nanopore. The nanopore surface charge can be derived from the acid‐base dissociation equilibrium of the modified polyelectrolyte. Various polyelectrolytes have been selected based on the acid dissociation constant of the monomer units, and various techniques have been applied to modify nanopores. However, they have been developed without clear guidelines for characterizing the surface modification status or surface charge. One reason has been the difficulty in accurately estimating the surface charge of nanopores in solution. Thus, in this study, the dissociation constant (pKaapp) of the surface charge of a modified polyelectrolyte nanopore was quantitatively estimated via electrochemical measurements. Previously, the modification status of nanopores has been evaluated using the ion current response. In addition, we monitored in real‐time the polyelectrolyte modification status using a quartz crystal microbalance (QCM). Some polyelectrolytes were difficult to immobilize directly on the nanopore surface, and those polymers could be effectively modified by the layer‐by‐layer (LbL) technique. Therefore, we produced a guideline for the fabrication of a nanopore sensor for pH measurements under physiological conditions by quantitative evaluation of the pKaapp via electrochemical methods, the monitoring of the modification status by QCM, and the development of an effective modification method via the LbL technique.
Recent advances in paper‐based preconcentrators by utilizing ion concentration polarization
Authors: Zhiyue Meng , Xichen Yuan , Li Ren , Yang Yang , Huicheng Feng , Peng Shang
Published: March 2021

One of the most cited limitations of biochemical detection is its poor sensitivity, owing to the relatively high complexity of micro‐samples. Moreover, some samples cannot be easily self‐replicated and their abundance cannot be increased through traditional technologies. Therefore, the preconcentration of low‐abundance samples is a key requirement for microfluidic biological analysis. In recent years, the ion‐concentration polarization phenomenon has aroused widespread interest in the application of microfluidic technology. In addition, paper‐based materials are readily available, easy to modify, and exhibit good hydrophilicity. The study of the ion‐concentration polarization preconcentration of micro‐samples in paper‐based microfluidic chips is of considerable significance. In this review, we discuss the development and applications of ion‐concentration polarization paper‐based preconcentrator in the past 5 years, with emphasis on key progresses in chip fabrication and performance optimization under different conditions. The current needs and development prospects in this field have also been discussed.
Smile‐implied hedging with volatility risk
Authors: François Pascal , Stentoft Lars
Published: March 2021

Options can be dynamically replicated using model‐free Greeks extracted from the volatility smile. However, smile‐implied delta and delta–gamma hedging do not achieve minimum variance in the presence of price–volatility correlation, and these strategies have shown poor performance relative to the Black–Scholes (BS) benchmark. We propose a way to extend smile‐implied option replication with volatility risk management. Large‐scale evidence on S&P 500 index options indicates that smile‐implied delta–gamma–vega hedging strategies outperform the BS approach as well as more sophisticated option hedging frameworks, including stochastic volatility and jumps.
An ensemble of daily simulated runoff data (1981–2099) under climate change conditions for 93 catchments in Switzerland (Hydro‐CH2018‐Runoff ensemble)
Authors: Muelchi Regula , Rössler Ole , Schwanbeck Jan , Weingartner Rolf , Martius Olivia
Published: March 2021

We present a new ensemble of daily runoff simulations for meso‐scale catchments in Switzerland for the period 1981–2099: The Hydro‐CH2018‐Runoff ensemble. The ensemble contains runoff simulations for 93 catchments in Switzerland covering a wide range of different catchment characteristics governed by pluvial, nival and glacial runoff regimes. The hydrological modelling system PREVAH was thoroughly calibrated and validated for each catchment. The simulations show satisfactory performance with a median Nash‐Sutcliffe efficiency of 0.82 in the calibration and validation period. The calibrated parameters were then used to simulate runoff under climate change for each of the 93 catchments. These simulations were driven by the high‐resolution new Swiss climate change scenarios (CH2018) consisting of 68 GCM‐RCM combinations covering 3 different emission scenarios: RCP2.6, RCP4.5 and RCP8.5. The simulations show good agreement between simulated and observed runoff regimes in the reference period. The Hydro‐CH2018‐Runoff ensemble is publicly available under http://doi.org/10.5281/zenodo.3937485 (Muelchi, R., Rössler, O., Schwanbeck, J., Weingartner, R., and Martius, O. (2020) Hydro‐CH2018‐Runoff ensemble (version v1). Zenodo) and can be used for further impact studies.
Comparative analysis of the effect of cell immobilization on the hydrogenothrophic biomethanation of CO2
Authors: Dağlıoğlu Tuğçe , Öğüt Tuba Ceren , Ozdemir Guven , Azbar Nuri
Published: March 2021

Carbon capture and utilization (CCU) has been offered as a potential technological solution for mitigating the greenhouse gas emissions and climate change concern worldwide. Anaerobically carbon utilization has started to be in the agenda of researchers in recent years since this approach offers significant advantages such as use of catalysis reactions through environmentally friendly microorganisms under low temperature and pressure operational conditions. Moreover, a cleaner and more effective bioenergy production is realized in the form of biomethane.

This study aimed to exploit the merits of cell immobilization in order to provide a stable hydrogenotrophic biomethanation process. For this purpose, two different immobilized bioreactors packed with plastic moving bed biofilm reactor (MBBR) and glass beads packing materials were comparatively investigated. To the best of our knowledge, these two immobilization materials were used for the first time for this purpose. Two different bioreactor configurations were compared for the performance parameters such as methane formation rate, H2 consumption and methane contents in the headspace. Methane content in the headspace of these bioreactors were measured to be 80 and 75% for MBBR bioreactor and glass bead bioreactors, respectively. In addition, methane formation rates (MFR) of 5.14 and 4.8 m3/m3/day were achieved in MBBR and glass beads bioreactors, respectively. Even though both bioreactor configurations performed highly efficient biomethanation of CO2, the statistical evaluation of the results indicated that MBBR performance was more favourable for hydrogenotrophic biomethanation. © 2021 Society of Chemical Industry and John Wiley & Sons, Ltd.
The future of the elderly population health status: Filling a knowledge gap
Authors: Atella Vincenzo , Belotti Federico , Kim Daejung , Goldman Dana , Gracner Tadeja , Piano Mortari Andrea , Tysinger Bryan
Published: March 2021

The aging process in OECD countries calls for a better understanding of the future disease prevalence, life expectancy (LE) and patterns of inequalities in health outcomes. In this paper we present the results obtained from several dynamic microsimulation models of the Future Elderly Model family for 12 OECD countries, with the aim of reproducing for the first time comparable long‐term projections in individual health status across OECD countries. We provide projections of LE and prevalence of major chronic conditions and disabilities, overall, by gender and by education. We find that the prevalence of main chronic conditions in Europe is catching‐up with the United States and significant heterogeneity in the evolution of gender and educational gradients. Our findings represent a contribution to support policymakers in designing and implementing effective interventions in the healthcare sector.
Hepcidin Signaling in Health and Disease: Ironing Out the Details
Authors: Kowdley Kris V. , Gochanour Eric M. , Sundaram Vinay , Shah Raj A. , Handa Priya
Published: March 2021

Hepcidin, a peptide hormone produced by hepatocytes, is the central regulator of systemic iron homeostasis through its interaction with ferroportin, the major cellular iron export protein. Hepcidin binding to ferroportin results in reduced iron export from macrophages and intestinal absorptive cells, leading to decreased serum iron levels. Hepcidin expression is influenced by several factors that include serum and liver iron stores, erythropoiesis, hypoxia, inflammation, and infection. Erythropoietic drive and hypoxia suppress hepcidin expression and promote red cell production. In contrast, inflammation and infection are associated with increased hepcidin production to sequester iron intracellularly as a means of depriving microorganisms of iron. Chronic inflammation may up-regulate hepcidin expression through the interleukin-6 (IL-6)–Janus kinase 2 (JAK2)–signal transducer and activator of transcription 3 (STAT3) pathway. The bone morphogenetic protein (BMP)–mothers against decapentaplegic homolog (SMAD) pathway is a major positive driver of hepcidin expression in response to either increased circulating iron in the form of transferrin or iron loading in organs. Hereditary hemochromatosis (HH) consists of several inherited disorders that cause inappropriately reduced hepcidin expression in response to body iron stores, leading to increased iron absorption from a normal diet. The most common form of HH is due to a mutation in the HFE gene, which causes a failure in the hepatocyte iron–sensing mechanism, leading to reduced hepcidin expression; the clinical manifestations of HFE-HH include increased serum transferrin–iron saturation and progressive iron loading in the liver and other tissues over time among patients who express the disease phenotype. In this article, we review the physiologic mechanisms and cellular pathways by which hepcidin expression is regulated, and the different forms of HH resulting from various mutations that cause hepcidin deficiency. We also review other drivers of hepcidin expression and the associated pathophysiologic consequences.
Non‐conventional fungicides to control dollar spot disease
Authors: Hsiang Tom , Stone Kate , Rudland Matt , Chen Jie
Published: March 2021

There are strong societal pressures against the use of synthetic pesticides in our modern urban society. The purpose of this work was to test the efficacy of several substances, many of which are household use items and can be considered non‐conventional, for their ability to control the common turfgrass disease, dollar spot, in lab and field tests. From the over 10 lab tests per treatment and the over 10 field tests between 2015 to 2019, we concluded that among over 20 mostly non‐conventional products applied at different rates and intervals, only ferrous sulfate (21% a.i.) used at 250 g per 100 m2 or ferric sulfate (84.5% a.i.) used at 300 g per 100 m2 applied in 10 L of water per 100 m2 on a weekly basis could provide suppression of dollar spot disease on creeping bentgrass equivalent to a standard fungicide control during periods of low to moderate disease pressure.
Influence of calcium and nitrogen fertilizer on creeping bentgrass infected with dollar spot under cool temperatures
Authors: Jiang Mingyan , Kaluwasha Waana , Xiong Xi
Published: March 2021

Dollar spot, caused by the fungal pathogen Clarireedia homoeocarpa Bennett, is a wide‐spread disease of creeping bentgrass (Agrostis stolonifera L.) that in the north central region of the U.S., occurs as early as March. Over‐dependence on fungicides has resulted in widespread resistance, necessitating non‐chemical treatment approaches. The objective of this experiment was to assess the effects of N and Ca fertilizers on creeping bentgrass for dollar spot tolerance under cool temperatures. In a chilling chamber, a single application of Ca or N fertilizer significantly reduced dollar spot disease cover by 47% or 34%, respectively, compared to the untreated control. Application of both Ca and N, however, appeared to be antagonistic and resulted in only a 14% reduction of disease cover. Application of Ca, not N, improved root production but reduced shoot growth in the 4‐week period regardless of dollar spot, resulting in an elevated root to shoot ratio. Root architecture, including total root length, surface area and total tips, was also improved following a Ca only application. Collectively, these results suggested that Ca might play a beneficial role in improving the stress tolerance of creeping bentgrass, and building healthier and stronger root systems in the spring‐like conditions. Although a single application of Ca does not adequately suppress dollar spot, future research might be of interest to explore optimal application strategies in order to reduce over‐dependence on fungicides.
A new device for selective mechanical broadleaf weed control in turfgrass
Authors: Henderson Jason J.
Published: March 2021

Weed control in turfgrass systems without herbicides can be challenging. Cost effective and reliable weed control options are needed in turfgrass systems managed organically or pesticide‐free. The objectives of this research were to determine i) the efficacy of selective, mechanical broadleaf weed control and ii) assess Weedbine injury potential in Poa pratensis L. (Kentucky bluegrass). This study was arranged in a randomized completed block design with two replications. The three treatments were: 1) Weedbine 1X wk–1, 2) synthetic herbicide, and 3) mow only control. Synthetic herbicides provided the quickest and most definitive level of weed control. However, the Weedbine used once per week immediately prior to mowing provided significantly higher weed control compared to the mow only control consistently throughout the growing season. Mechanically treated plots exhibited some turfgrass injury following treatments in August and September. However, mechanically treated plots had higher turfgrass quality than herbicide‐treated plots in November due to subsequent weed encroachment in herbicide treated plots later in the growing season. The Weedbine has potential for applying selective, mechanical weed control with minimal injury in Poa pratensis.
Survival of Staphylococcus aureus applied to Poa pratensis L. and synthetic turf
Authors: McNitt Andrew S. , Petrunak Dianne M. , Serensits Thomas J.
Published: March 2021

Methicillin resistant Staphylococcus aureus (MRSA) isolates have become more prevalent among athletes. The objective of this study is to examine the survival of S. aureus on synthetic turf systems and natural turfgrass under varying environmental conditions and to evaluate the effectiveness of various control agents applied to the synthetic turf. Under non‐extreme temperature and very limited light conditions, less than 4% of the S. aureus applied survived on both synthetic and natural turfgrass for 12 d. Applied control agents reduced survival rates to less than 1% survival at 6 d for all but one treatment. When S. aureus was applied to outdoor surfaces in the presence of sunlight, the bacterial survival rate was reduced to under 1% survivability within 2 h of S. aureus application on synthetic turf and within 3 h on natural turfgrass. Exposure to UV light and higher temperature seemed to be an effective disinfectant under the conditions of this experiment. Survival rates on synthetic and natural turfgrass did not differ greatly in indoor conditions.
Effects of growing degree day based trinexapac‐ethyl application on ultradwarf hybrid bermudagrass putting green quality and ball roll
Authors: Carroll Devon E. , Brosnan James T. , Reasor Eric H. , Kerns James P. , Stephens Cameron M. , Horvath Brandon J. , Dickson Kyley H. , Tomaso‐Peterson Maria
Published: March 2021

Application of plant growth regulators to hybrid bermudagrass [Cynodon dactylon (L.) Pers. × Cynodon transvaalensis Burtt Davy] putting greens is a common management practice used to reduce clipping yield and improve aesthetic and functional turfgrass quality. Growing degree day (GDD) models have explored the effects of plant growth regulator application timing on ultradwarf hybrid bermudagrass clipping yield. However, there is a need for research evaluating effects of GDD‐timed plant growth regulator applications on turfgrass quality and ball roll. A field study was conducted in summer 2018 at three locations (Knoxville, TN; Raleigh, NC; and Starkville, MS) to determine the effects of trinexapac‐ethyl (TE) applied according to a GDD model on ultradwarf hybrid bermudagrass putting green quality and ball roll compared to calendar‐based treatment (i.e., weekly or twice‐weekly). For GDD applications, TE was applied at either 20 or 33 g ha−1. GDD based applications were made once 220 GDD (base 10°C) accumulated after each treatment. TE was applied at either 20 or 33 g ha−1 for weekly treatments and rate reduced to either 14 or 16 g ha−1 for the twice‐weekly treatment. In all locations, TE applied on a 220 GDD10C schedule resulted in turfgrass quality greater than or equal to that of the weekly and twice‐weekly applied treatments. Ball roll distance was slightly lower in plots treated with TE every 220 GDD10C compared to the weekly and twice‐weekly treatments, although differences may be negligible to golfers (13 to 23 cm). Ball roll distance was negatively correlated with clipping yield (−0.37 to −0.69). Turfgrass managers choosing to regulate ultradwarf hybrid bermudagrass greens with TE should consider applying on a GDD rather than calendar‐based interval to achieve improved turfgrass quality without sacrificing ball roll distance.