bluuebunny/crossref_metadata_2025 huggingface dataset:
On‐off‐on Control of Molecular Inversion Symmetry via Multi‐stage Protonation: Elucidating Vibronic Laporte Rule
Authors: Stark Charles W. , Rammo Matt , Trummal Aleksander , Uudsemaa Merle , Pahapill Juri , Sildoja Meelis‐Mait , Tshepelevitsh Sofja , Leito Ivo , Young David C. , Szymański Bartosz , Vakuliuk Olena , Gryko Daniel T. , Rebane Aleksander
Published: October 2022

The Laporte rule dictates that one‐ and two‐photon absorption spectra of inversion‐symmetric molecules should display alternatively forbidden electronic transitions; however, for organic fluorophores, drawing clear distinction between the symmetric‐ and non‐inversion symmetric two‐photon spectra is often obscured due to prevalent vibronic interactions. We take advantage of consecutive single‐ and double‐protonation to break and then reconstitute inversion symmetry in a nominally symmetric diketopyrrolopyrrole, causing large changes in two‐photon absorption. By performing detailed one‐ and two‐photon titration experiments, with supporting quantum‐chemical model calculations, we explain how certain low‐frequency vibrational modes may lead to apparent deviations from the strict Laporte rule. As a result, the system may be indeed considered as an on‐off‐on inversion symmetry switch, opening new avenues for two‐photon sensing applications.
A Sustainable NH4+Ion Battery by Electrolyte Engineering
Authors: Tian Zhengnan , Yin Jun , Guo Tianchao , Zhao Zhiming , Zhu Yunpei , Wang Yizhou , Yin Jian , Zou Yeguo , Lei Yongjiu , Ming Jun , Bakr Osman , Mohammed Omar F. , Alshareef Husam N.
Published: October 2022

Aqueous ammonium ion battery is a promising sustainable energy storage system. However, the side reactions originating from electrolytes (the water decomposition and host material dissolution) preclude its practical applications. Unlike the metal‐based aqueous batteries, the idea of “ultrahigh concentrated electrolyte” is not feasible due to the strong hydrolysis of ammonium ions. Therefore, we propose an effective and sustainable strategy for the water hydrogen bond network modulation by adding sucrose into the electrolytes. The sucrose can form sucrose‐water hydrogen bond networks to break the continuous water hydrogen bond network, thereby inhibiting water decomposition significantly. Moreover, the weak hydrogen bond interaction between ammonium and sucrose facilitates rapid ion migration, leading to an improved ionic conductivity. This work presents a new electrolyte modulating strategy for the practical application of aqueous ammonium ion batteries.
Organic Zinc‐Ion Battery: Planar, π‐Conjugated Quinone‐Based Polymer Endows Ultrafast Ion Diffusion Kinetics
Authors: Ye Fei , Liu Qiang , Dong Hongliang , Guan Kailin , Chen Zhaoyang , Ju Na , Hu Linfeng
Published: October 2022

A novel poly(phenazine‐alt‐pyromellitic anhydride) (PPPA) has been successfully designed and synthesized via a condensation polymerization strategy as promising cathode material in organic zinc‐ion batteries. Electrochemical quartz crystal microbalance (EQCM), FTIR and XPS characterizations verify a reversible Zn2+‐coordination mechanism in our PPPA cathode. Intriguingly, an ultrahigh Zn2+diffusion coefficient of 1.2×10−7 cm2 s−1was found in this large π‐conjugated system, which is the highest one among all organic cathode materials for zinc‐ion batteries. Theoretical calculations reveal the extended π‐conjugated plane in our PPPA sample results in a significant reduction on energy gap, effectively accelerating intramolecular electron transfer during charge/discharge process. Our finding provides insights to achieve high zinc‐ion transport kinetics by a design strategy on planar polymer system.
Competitive Non‐Radical Nucleophilic Attack Pathways for NH3 Oxidation and H2O Oxidation on Hematite Photoanodes
Authors: Wu Lei , Tang Daojian , Xue Jing , Liu Siqin , Wang Jiaming , Ji Hongwei , Chen Chuncheng , Zhang Yuchao , Zhao Jincai
Published: October 2022

The sluggish H2O oxidation kinetics on photoanodes severely obstructs the overall solar‐to‐energy efficiency of photoelectrochemical (PEC) cells. Herein, we find a 10 to 55‐fold increase of photocurrent by conducting ammonia oxidation reaction (AOR) on hematite (α‐Fe2O3) photoanodes under near‐neutral pH (9–11) and moderate applied potentials (1.0–1.4 VRHE) compared to H2O oxidation. By rate law analysis and operando spectroscopic studies, we confirm the non‐radical nucleophilic attack of NH3 molecules on high‐valent surface Fe−O species (e.g., FeIV=O) and Fe−N species that produces NOx− and N2, respectively, which overwhelms the nucleophilic attack of H2O on surface FeIV=O and contributes to a high Faradaic efficiency of above 80 % for AOR. This work reveals a novel non‐radical nucleophilic attack strategy, which is significantly different from the conventional indirect radical‐mediated AOR mechanism, for the rational design of high‐performance AOR photoelectrocatalysts.
Gold(I) Multi‐Resonance Thermally Activated Delayed Fluorescent Emitters for Highly Efficient Ultrapure‐Green Organic Light‐Emitting Diodes
Authors: Cai Siyuan , Tong Glenna So Ming , Du Lili , So Gary Kwok‐Ming , Hung Faan‐Fung , Lam Tsz‐Lung , Cheng Gang , Xiao Hui , Chang Xiaoyong , Xu Zong‐Xiang , Che Chi‐Ming
Published: October 2022

Acceleration of singlet‐triplet intersystem crossings (ISC) is instrumental in bolstering triplet exciton harvesting of multi‐resonance thermally activated delayed fluorescent (MR‐TADF) emitters. This work describes a simple gold(I) coordination strategy to enhance the spin‐orbit coupling of green and blue BN(O)‐based MR‐TADF emitters, which results in a notable increase in rate constants of the spectroscopically observed ISC process to 3×109 s−1 with nearly unitary ISC quantum yields. Accordingly, the resultant thermally‐stable AuI emitters attained large values of delayed fluorescence radiative rate constant up to 1.3×105/1.7×105 s−1 in THF/PMMA film while preserving narrowband emissions (FWHM=30–37 nm) and high emission quantum yields (ca. 0.9). The vapor‐deposited ultrapure‐green OLEDs fabricated with these AuI emitters delivered high luminance of up to 2.53×105 cd m−2 as well as external quantum efficiencies of up to 30.3 % with roll‐offs as low as 0.8 % and long device lifetimes (LT60) of 1210 h at 1000 cd m−2.
Organizing Enzymes on Self‐Assembled Protein Cages for Cascade Reactions
Authors: Kang Wei , Ma Xiao , Kakarla Deepika , Zhang Huawei , Fang Yunming , Chen Baizhu , Zhu Kongfu , Zheng Danni , Wu Zhiyue , Li Bo , Xue Chuang
Published: October 2022

Cells use self‐assembled biomaterials such as lipid membranes or proteinaceous shells to coordinate thousands of reactions that simultaneously take place within crowded spaces. However, mimicking such spatial organization for synthetic applications in engineered systems remains a challenge, resulting in inferior catalytic efficiency. In this work, we show that protein cages as an ideal scaffold to organize enzymes to enhance cascade reactions both in vitro and in living cells. We demonstrate that not only enzyme‐enzyme distance but also the improved Km value contribute to the enhanced reaction rate of cascade reactions. Three sequential enzymes for lycopene biosynthesis have been co‐localized on the exterior of the engineered protein cages in Escherichia coli, leading to an 8.5‐fold increase of lycopene production by streamlining metabolic flux towards its biosynthesis. This versatile system offers a powerful tool to achieve enzyme spatial organization for broad applications in biocatalysis.
Novel aldo–keto reductase AKR2E9 regulates aldehyde content in the midgut and antennae of the silkworm (Bombyx mori)
Authors: Yamamoto Kohji , Endo Satoshi
Published: October 2022

We studied the effects of green leaf volatiles (including reactive aldehydes) emitted by plants on insects that feed on these plants. The silkworm (Bombyx mori) is a model lepidopteran that eats mulberry leaves. Defense‐related enzymes in silkworms can be targeted for developing new pest control methods. The aldo–keto reductase (AKR) superfamily catalyzes aldehyde reduction by converting a carbonyl group into an alcohol group. Here, we characterized a novel silkworm AKR, designated as AKR2E9. Recombinant AKR2E9 was overexpressed in Escherichia coli. The recombinant protein was used, along with nicotinamide adenine dinucleotide phosphate as a coenzyme, to reduce aldehydes present in mulberry (Morus alba) leaves. The catalytic efficiency of AKR2E9 toward various aldehyde substrates and its inhibitor sensitivity was lower than those of AKR2E8. High expression levels of akr2e9 messenger RNA (mRNA) were detected in the midgut and antennae of silkworms. In the antennae of adult silkworms, akr2e9 mRNA was more abundant than akr2e8 mRNA. The catalytic efficiency of AKR2E9 was low because of steric hindrance, due to which its active site is blocked. High expression levels of AKR2E9 in the midgut and antennae suggest that it may regulate the detoxification of toxic aldehydes in silkworms.
A structural equation model analysis of the relationship between maternal fear of childbirth and expectant fathers’ fear of childbirth: The mediating role of fathers’ depression, anxiety, and stress
Authors: Ghaffari Seyedeh Fatemeh , Elyasi Forouzan , Nikbakht Roya , Shahhosseini Zohreh
Published: October 2022

Introduction

Some fathers experience traumatic and unpleasant feelings such as fear of childbirth during pregnancy and childbirth. This study aimed to determine the mediating role of the expectant fathers’ depression, anxiety, and stress in the relationship between maternal fear of childbirth and paternal fear of childbirth.

Methods

In this cross‐sectional study, using a two‐stage sampling method, 502 expectant Iranian fathers and their wives in the second half of pregnancy were recruited. The participants completed self‐administered questionnaires, including the fathers’ fear of childbirth scale, the Wijma delivery expectancy/experience questionnaire, and the depression, anxiety, and stress scale‐21. To analyze the data, structural equation modeling was employed in the Amos software version 24.

Results

Results indicated an acceptable fit of the model to the data. Maternal fear of childbirth was associated with paternal fear of childbirth, directly (β = 0.23, p = .046) and indirectly through the mediator of paternal depression, anxiety, and stress (β = .17, p = .007). The expectant fathers’ stress had a greater impact on their fear of childbirth.

Conclusions

By considering the role of maternal fear of childbirth as well as expectant fathers’ depression, anxiety, and stress on paternal fear of childbirth, it seems this study has some practical implications for improving the fathers’ psychological well‐being.
Greening the business: How ambidextrous companies succeed in green innovation through to sustainable development
Authors: Cancela Beatriz Lopes , Coelho Arnaldo , Duarte Neves Maria Elisabete
Published: October 2022

This paper seeks to investigate the impact of ambidexterity (exploration and exploitation) on green product innovation and the success of new products through the effects of sustainability, considering the moderating role of customer pressure. This research proposes a theoretical model that was tested using structural equation modelling (SEM) and a multigroup analysis to understand the moderating role of customer pressure. A 23‐item questionnaire was developed to explore the proposed relationships, applied in two different moments, answered by two other critical respondents from each company. At the end of the second collection moment, 336 valid questionnaires were collected from a sample of industrial SMEs in Portugal. The results show a positive influence of ambidexterity on sustainability and, therefore, on new product success and green product innovation. In addition, green product innovation increases the success of new products due to the growing demand for more sustainable products. Furthermore, the chain of effects between ambidexterity and further product success was strengthened when customer pressure was higher. This study stresses the need to actively manage exploration and exploitation investments to enhance ambidexterity, especially when sustainability and green innovation are the expected outcomes. The originality of this research is related to the contributions of hierarchical dynamic capabilities, combining and balancing exploration and exploitation, to produce successful ambidextrous companies in sustainability and green strategies.
The role of place in shaping responsibility logics: Revisiting the relation between place and business sustainability
Authors: Hermelingmeier Verena , Augenstein Karoline , Palzkill Alexandra
Published: October 2022

Place has been suggested to play a role for the sustainability orientation in business. A research gap exists in zooming in further on this relationship and in analysing how the organizational sense of place influences such an orientation. Applying the conceptual lens of institutional logics, we operationalize sustainability orientation as hybrid responsibility logic and analyse the role of place in the forming of such a logic. We present the results of a case study of businesses from a local sustainability network in the German city of Wuppertal and surroundings. Based on qualitative interview data, we found place to function as a coping mechanism in dealing with conflicting logics in the context of sustainability challenges. Across four heuristic types, we describe different roles of place in shaping responsibility logics: from providing the scenery for philanthropic engagement to being the nucleus for transformational efforts.
Cyclin‐dependent kinase subunit2 (CKS2) promotes malignant phenotypes and epithelial‐mesenchymal transition‐like process in glioma by activating TGFβ/SMAD signaling
Authors: Feng Fan , Zhao Zongqing , Cai Xuechang , Heng Xueyuan , Ma Ximeng
Published: October 2022

Background

Gliomas are a group of primary intracranial tumors with high morbidity and mortality. The previous researches indicated a crucial role of CKS2 (cyclin‐dependent kinases regulatory subunit 2) in hepatocellular carcinoma and breast cancer; however, little is known about the molecular mechanism of CKS2 in the tumorigenesis and epithelial‐mesenchymal transition‐like (EMT) process in glioma.

Methods

Datasets for bioinformatics analysis were obtained from the GEO, TCGA and CGGA databases. qRT‐PCR, western blotting (WB), and immunohistochemistry (IHC) assays were used to investigate the expression patterns of CKS2 among glioma and brain tissues. Glioma cells were transfected with small interfering RNA/overexpression plasmid against CKS2, then clone formation assay, CCK‐8, wound healing, Transwell assay, and flow cytometry were performed to detect changes in cell viability, invasiveness, and the apoptosis rate. Markers of cell invasion, apoptosis, EMT and TGFβ/SMAD signaling were evaluated by WB and immunofluorescence (IF) assays.

Results

We found that CKS2 overexpression correlates with poor prognosis in human glioma and knockdown of CKS2 could inhibit cell proliferation, migration, invasion, and induced apoptosis in glioma cells. Besides, we also found that knockdown of CKS2 could reverse the EMT process via modulating EMT‐related molecules. Glioma cells with overexpression of CKS2 were constructed to confirmed the fact that CKS2 induced nucleocytoplasmic translocation of SMAD2/3 and activated TGFβ/SMAD pathway, then upregulated its downstream targets expression, while inhibition of TGFβ/SMAD (by TGFβ inhibitor LY2157299 or SMAD4 siRNA) could reverse the tumor‐promoting effects and malignant phenotype caused by CKS2 overexpression.

Conclusions

We identified CKS2 as a critical contributor to the gliomagenesis, which might provide a novel therapeutic target for inhibiting the spread and infiltration of glioma.
Notch signaling‐induced cyclin d1 in diabetes ameliorating effects of the isolated polysaccharide from Rosa canina: In vitro and in vivo studies
Authors: Sajadimajd Soraya , Bahrami Gholamreza , Mohammadi Bahareh , Madani Seyed Hamid
Published: October 2022

Notch signaling has a role in the expansion of the pancreas and the pathogenesis of diabetes. Modulation of Notch signaling by natural products seems to pave the way for treating diabetes. This research aimed to scrutinize the involvement of the Notch cascade in the diabetes‐ameliorating effects of an isolated polysaccharide from Rosa canina. The isolated polysaccharide was characterized using Fourier transform infrared, nuclear magnetic resonance, high‐performance gel‐permeation chromatography, and liquid chromatography with tandem mass spectrometry techniques. Rat pancreatic β cells and STZ‐induced diabetic rats were treated with the isolated polysaccharide. MTT assay, cell cycle analysis, quantative realtime‐polymerase chain reaction, immunohistochemistry, and immunoblotting were used to reveal the growth and the expression levels of Notch1, DLL4, Jagged‐1, hes1, Ins‐1, Pdx‐1, and cyclin d1 in treated and untreated pancreatic cells and tissues. The ameliorating effect of the polysaccharide in STZ‐treated cells was accomplished by upregulation of cyclin d1 and hes1 as well as cell cycle progression. Notch inhibition by LY‐411575 was associated with the downregulation of cyclin d1 which upregulates with polysaccharide treatment. The significant expression of cyclin d1 (90%) and nuclear expression of hes1 in the pancreas of the polysaccharide group were accompanied by improvement of hyperglycemia and associated biochemical factors as well as regeneration of islet cells as compared to untreated diabetic rats. Based on these findings, upregulation of Notch signaling‐induced cyclin d1 could be proposed as the underlying diabetes‐reducing effects of the isolated polysaccharide derivative implying that cyclin d1 actuation through activation of the Notch‐DLL4 circuit may play the causal role in the treatment of diabetes.
Coordination Engineering of Single‐Atom Iron Catalysts for Oxygen Evolution Reaction
Authors: Yang Weijie , Zhou Binghui , Jia Zhenhe , Wu Chongchong , Wei Li , Gao Zhengyang , Li Hao
Published: October 2022

Developing highly active oxygen evolution reaction (OER) catalyst is essential to improve the performance of a water electrolyzer, where single‐atom catalysts (SACs) have shown promising performance in recent years. However, while SACs with various coordination environment have become experimentally feasible, knowledge about the structure‐performance relationship of SACs is still very limited, especially for the emerging multiple p‐block element‐doped SACs substrates. Herein, by adjusting the coordination environment of single‐atom iron catalysts, 122 SACs with various substrates were designed for comprehensive analysis. Through spin‐polarized density functional theory calculations with van der Waals corrections, 52 stable single‐atom iron catalysts were identified. To analyze their OER performance, an OER volcano activity model was derived to predict their performance as the function of O* and HO* binding free energies. Interestingly, a Fe1B1C1N2‐pen structure was found to have an outstanding OER activity (with a theoretical overpotential of 0.40 V vs. reversible hydrogen electrode) due to its unique adsorption mode that strengthens HO‐bonding by forming the Fe−OH−B bond. Based on these results, the OER performance of 26 TM1/B1C1N2‐pen (TM=Ti−Zn, Zr−Cd, and Hf−Au) SACs were determined based on this unique coordination environment by B‐doping. Most importantly, this study shows that the OER performance of SACs can be significantly improved by tuning the coordination environment of an active metal center.
Effects of Structured 3D Electrodes on the Performance of Redox Flow Batteries
Authors: De Wolf Renée , De Rop Michiel , Hereijgers Jonas
Published: October 2022

Invited for this issue's Front Cover is the Research group Applied Electrochemistry & Catalysis of the University of Antwerp. The cover picture shows an exploded view of the redox flow battery used to study the influence of structured 3D electrodes and how they can control the flow profile of the electrolyte. Read the full text of the Research Article at 10.1002/celc.202200640.
Optimization of G‐Quadruplex Ligands through a SAR Study Combining Parallel Synthesis and Screening of Cationic Bis(acylhydrazones)
Authors: Reznichenko Oksana , Leclercq Denis , Franco Pinto Jaime , Mouawad Liliane , Gabelica Valérie , Granzhan Anton
Published: October 2022

G‐quadruplexes (G4s), secondary structures adopted by guanine‐rich DNA and RNA sequences, are implicated in numerous biological processes and have been suggested as potential drug targets. Accordingly, there is an increasing interest in developing high‐throughput methods that allow the generation of congeneric series of G4‐targeting molecules (“ligands”) and investigating their interactions with the targets. We have developed an operationally simple method of parallel synthesis to generate “ready‐to‐screen” libraries of cationic acylhydrazones, a motif that we have previously identified as a promising scaffold for potent, biologically active G4 ligands. Combined with well‐established screening techniques, such as fluorescence melting, this method enables the rapid synthesis and screening of combinatorial libraries of potential G4 ligands. Following this protocol, we synthesized a combinatorial library of 90 bis(acylhydrazones) and screened it against five different nucleic acid structures. This way, we were able to analyze the structure–activity relationships within this series of G4 ligands, and identified three novel promising ligands whose interactions with G4‐DNAs of different topologies were studied in detail by a combination of several biophysical techniques, including native mass spectrometry, and molecular modeling.
Tetra(peri‐naphthylene)anthracene: A Near‐IR Fluorophore with Four‐Stage Amphoteric Redox Properties
Authors: Frisch Sabine , Neiß Christian , Lindenthal Sebastian , Zorn Nicolas F. , Rominger Frank , Görling Andreas , Zaumseil Jana , Kivala Milan
Published: October 2022

A novel, benign synthetic strategy towards soluble tetra(peri‐naphthylene)anthracene (TPNA) decorated with triisopropylsilylethynyl substituents has been established. The compound is perfectly stable under ambient conditions in air and features intense and strongly bathochromically shifted UV/vis absorption and emission bands reaching to near‐IR region beyond 900 nm. Cyclic voltammetry measurements revealed four facilitated reversible redox events comprising two oxidations and two reductions. These remarkable experimental findings were corroborated by theoretical studies to identify the TPNA platform a particularly useful candidate for the development of functional near‐IR fluorophores upon appropriate functionalization.
Aufreinigung von Nano‐ und Submikronpartikeln durch präparative Gelelektrophorese
Authors: Barasinski Matthäus , Garnweitner Georg
Published: October 2022

Die präparative Gelelektrophorese ermöglicht die Auftrennung von Nano‐ und Submikronpartikeln auf Basis ihrer unterschiedlichen elektrophoretischen Mobilität. Es wird gezeigt, dass eine Trennung der Partikel nicht nur nach der Partikelgröße, sondern auch nach Oberflächenladung bzw. Oberflächenchemie und Morphologie möglich ist. Während diese Methode analog zum Einsatz in der Biotechnologie bislang auf kleine Mengen beschränkt ist, werden Möglichkeiten für eine Steigerung des Partikeldurchsatzes sowie die kontinuierliche Trennung aufgezeigt.
Der Frosch, der aus der Kälte kam
Authors: Tetsch Larissa
Published: October 2022

Der Waldfrosch lebt in den feuchten Wäldern Nordamerikas, in denen die Temperaturen im Winter deutlich unter den Gefrierpunkt fallen. Für den Frosch kein Problem: Mit Hilfe eines körpereigenen Frostschutzmittels kann er einige Zeit im gefrorenen Zustand überleben.
Beginner's Guide to Raman Spectroelectrochemistry for Electrocatalysis Study
Authors: Zheng Weiran
Published: October 2022

The need for continuous observation of electrocatalytic processes under operating conditions has promoted the popularity of in situ techniques coupled with electrochemical tests. In situ Raman spectrometer coupled with electrochemistry (or Raman spectroelectrochemistry) is a powerful tool to provide real‐time structural information related to the dynamic electrolyte/electrode interface. To make it more accessible among the electrocatalysis community, we provide an essential experimental guideline of in situ Raman spectroelectrochemistry to beginners. After the necessary background of the technical principle and primary applications, we focus on the experimental considerations, from electrode preparation, cell design, and laser parameters to the electrochemical sequence and data process. The recent efforts to make this technique more affordable are also highlighted. We hope this review can help beginners to understand and use Raman spectroelectrochemistry.
Low‐Temperature Thermal Formation of the Cyclic Methylphosphonic Acid Trimer [c‐(CH3PO2)3]
Authors: Zhang Chaojiang , Turner Andrew M. , Wang Jia , Marks Joshua H. , Fortenberry Ryan C. , Kaiser Ralf I.
Published: October 2022

We report the formation of the cyclic methylphosphonic acid trimer [c‐(CH3PO2)3] through condensation reactions during thermal processing of low‐temperature methylphosphonic acid samples exploiting photoionization reflectron time‐of‐flight mass spectrometry (PI−ReTOF−MS) along with electronic structure calculations. Cyclic methylphosphonic acid trimers are formed in the solid state and detected together with its protonated species in the gas phase upon single photon ionization. Our studies provide an understanding of the preparation of phosphorus‐bearing potentially prebiotic molecules and the fundamental knowledge of low‐temperature phosphorus chemistry in extraterrestrial environments.
Cochlear hair cell innervation is dependent on a modulatory function of Semaphorin‐3A
Authors: Cantu‐Guerra Homero L. , Papazian Michael R. , Gorsky Anna L. , Alekos Nathalie S. , Caccavano Adam , Karagulyan Nare , Neef Jakob , Vicini Stefano , Moser Tobias , Coate Thomas M.
Published: October 2022

Background

Proper connectivity between type I spiral ganglion neurons (SGNs) and inner hair cells (IHCs) in the cochlea is necessary for conveying sound information to the brain in mammals. Previous studies have shown that type I SGNs are heterogeneous in form, function and synaptic location on IHCs, but factors controlling their patterns of connectivity are not well understood.

Results

During development, cochlear supporting cells and SGNs express Semaphorin‐3A (SEMA3A), a known axon guidance factor. Mice homozygous for a point mutation that attenuates normal SEMA3A repulsive activity (Sema3aK108N) show cochleae with grossly normal patterns of IHC innervation. However, genetic sparse labeling and three‐dimensional reconstructions of individual SGNs show that cochleae from Sema3aK108N mice lacked the normal synaptic distribution of type I SGNs. Additionally, Sema3aK108N cochleae show a disrupted distribution of GLUA2 postsynaptic patches around the IHCs. The addition of SEMA3A‐Fc to postnatal cochleae led to increases in SGN branching, similar to the effects of inhibiting glutamate receptors. Ca2+ imaging studies show that SEMA3A‐Fc decreases SGN activity.

Conclusions

Contrary to the canonical view of SEMA3A as a guidance ligand, our results suggest SEMA3A may regulate SGN excitability in the cochlea, which may influence the morphology and synaptic arrangement of type I SGNs.
How environmental regulation can drive innovation: Lessons learned from a systematic review
Authors: Clausen Lauge Peter Westergaard , Nielsen Maria Bille , Oturai Nikoline Bang , Syberg Kristian , Hansen Steffen Foss
Published: October 2022

Regulation is often seen as a barrier to innovation. However, if done properly, it can actually serve as a driver of innovation. To understand how environmental regulation can be designed to stimulate innovation, we scrutinise the scientific literature related to regulation, innovation and the environment. Fifty one carefully selected studies are examined with regard to their scope, results and geographical affiliation, and their findings were distilled into ten lessons on how to design environmental regulation to stimulate innovation. Subsequently, we discuss the validity and implications of the lessons. We find that the lessons are overarching concepts of principal nature that are applicable for most regulatory settings. We also find that recent EU regulations on plastics, nanomaterials and waste support many of the lessons learned, while some are completely neglected. The lessons offer important guidance and can be seen as a checklist of what regulators must consider when designing new regulation.
Pressures do not equal volumes: implications for heart failure management in patients with CardioMEMS
Authors: Khan Muhammad Shahzeb , Khouri Michel G. , Gomez Leilani , Fudim Marat
Published: October 2022

Pulmonary arterial pressures are often used as surrogates for intravascular blood volume. However, the relationship between pressure and volume remains controversial. To contextualize and provide concrete examples and impact on clinical management, we report two cases of heart failure (one in heart failure with reduced ejection fraction and one in heart failure with preserved ejection fraction) where pressure‐based measurements did not accurately represent the intravascular status and affected clinical management.
Latent Carbene: Diaminomethylation of Thiophenes
Authors: Koidan Georgyi , Hurieva Anastasiya , Zahorulko Serhii , Zadorozhny Alexander , Lysenko Viacheslav , Shvydenko Tetiana , Rusanov Eduard B. , Kostyuk Aleksandr
Published: October 2022

The reaction of silylformamidine with various halo‐ and ethoxycarbonyl substituted thiophenes was studied. It proceeded via C−H bond insertion of the nucleophilic diaminocarbene that exists in an equilibrium with silylformamidine affording aminals. The reaction proceeded more readily at the 2(5)‐position compared to the 3(4) one. The number of halogens at the thiophenes markedly influences the reaction. The more halogens, the higher the reaction rate. Even one electron acceptor group at the thiophene ring is enough to promote the reaction. As a rule, the reaction does not require solvents or catalysts. Hydrolyses of the aminals provides a novel convenient approach to substituted thiophene aldehydes.
Total Synthesis of Calcaripeptide C
Authors: Patil Shashikant , Mali Maruti , Ghosh Subhash
Published: October 2022

Total synthesis of marine cyclodepsipeptide calcaripeptide C, isolated from Calcarisporium sp. Strain KF525 is reported. In the present strategy the macrocycle was constructed through ring‐closing metathesis reaction which makes the synthesis more convergent.
An illustration of model agnostic explainability methods applied to environmental data
Authors: Wikle Christopher K. , Datta Abhirup , Hari Bhava Vyasa , Boone Edward L. , Sahoo Indranil , Kavila Indulekha , Castruccio Stefano , Simmons Susan J. , Burr Wesley S. , Chang Won
Published: October 2022

Historically, two primary criticisms statisticians have of machine learning and deep neural models is their lack of uncertainty quantification and the inability to do inference (i.e., to explain what inputs are important). Explainable AI has developed in the last few years as a sub‐discipline of computer science and machine learning to mitigate these concerns (as well as concerns of fairness and transparency in deep modeling). In this article, our focus is on explaining which inputs are important in models for predicting environmental data. In particular, we focus on three general methods for explainability that are model agnostic and thus applicable across a breadth of models without internal explainability: “feature shuffling”, “interpretable local surrogates”, and “occlusion analysis”. We describe particular implementations of each of these and illustrate their use with a variety of models, all applied to the problem of long‐lead forecasting monthly soil moisture in the North American corn belt given sea surface temperature anomalies in the Pacific Ocean.
A cross‐sectional study on food safety knowledge and practices among food handlers in tertiary and second circle institutions in Ho municipality, Ghana
Authors: Madilo Felix Kwashie , Letsyo Emmanuel , Klutse Comfort Mawuse
Published: October 2022

In recent years, incidences of food poisoning have been reported in some schools across the country. However, little attention has been paid to the hygiene practices of food vendors in the schools. This study, therefore, investigates the food safety knowledge and practices of food vendors catering for tertiary and second cycle students in the Ho municipality. The piloted and validated questionnaire used to sample 608 respondents revealed that the majority of the respondents sampled were female (76.0%), between the ages of 26 and 40 (51%), married (47.4%), and have tertiary or senior high school certificate (60.7%). They have been in business for not more than 2 years (36.2%) and had neither food safety (62.3%) nor good manufacturing practice (81.9%) training. However, they have sufficient knowledge in food safety regarding purchasing, storage, cooking and reheating, and personal hygiene, but exhibited poor knowledge and practice of food temperature control protocols. Both Kendall's tau‐b coefficient correlation and linear regression model revealed a significant positive correlation between food safety knowledge and practices of the vendors. Nevertheless, regular training and monitoring are necessary to enable the vendors to fully implement the food temperature control protocols, which is one of the major causes of food poisoning in the country.
Observing cognitive processes in time through functional MRI model comparison
Authors: Marxen Michael , Graff Johanna E. , Riedel Philipp , Smolka Michael N.
Published: October 2022

The temporal specificity of functional magnetic resonance imaging (fMRI) is limited by a sluggish and locally variable hemodynamic response trailing the neural activity by seconds. Here, we demonstrate for an attention capture paradigm that it is, never the less, possible to extract information about the relative timing of regional brain activity during cognitive processes on the scale of 100 ms by comparing alternative signal models representing early versus late activation. We demonstrate that model selection is not driven by confounding regional differences in hemodynamic delay. We show, including replication, that the activity in the dorsal anterior insula is an early signal predictive of behavioral performance, while amygdala and ventral anterior insula signals are not. This specific finding provides new insights into how the brain assigns salience to stimuli and emphasizes the role of the dorsal anterior insula in this context. The general analytic approach, named “Cognitive Timing through Model Comparison” (CTMC), offers an exciting and novel method to identify functional brain subunits and their causal interactions.
Health literacy status of pregnant women and women with young children in Tasmania
Authors: Melwani Satish , Cleland Verity , Patterson Kira , Nash Rosie
Published: October 2022

Issue Addressed

The literature provides evidence that maternal health is strongly linked with noncommunicable diseases (NCDs) and their associated risk factors. Enabling women with the asset of health literacy may help to reduce the intergenerational impact of NCDs. However, little is known about the health literacy of pregnant women and women with young children in Tasmania and globally. This study aimed to identify the health literacy status of pregnant women and women with young children (0‐8 years) living in Tasmania and describe their health literacy status according to their demographic characteristics.

Methods

An online cross‐sectional survey was undertaken. The survey included demographic questions and a health literacy questionnaire (HLQ). The description of demographic differences across the HLQ scales focused on effect sizes (ES) for standardised differences in mean health literacy scores. The differences found to be statistically significant at P < 0.05 were also included.

Results

194 participants completed the survey with a mean age of 35.3 years. 73.2% were married, 16.5% were pregnant, 93% had one or more children and 81.5% were university educated. For the first five HLQ scales (score range 1‐4), the lowest overall score was seen for the scale “Actively managing my health” (mean = 2.96; SD = 0.54). For the last four scales (score range 1‐5), the lowest overall score was seen for the scale “Navigating the health care system” (mean = 3.75, SD = 0.67). Nonpregnant women, women with children, women with chronic health conditions and nonmarried women experienced more health literacy challenges.

Conclusion

Women in our study showed various strengths and challenges with mean scores varying across the nine HLQ scales. Understanding the health literacy needs of women will enable health services to co‐design solutions and interventions capable of responding to the evolving health needs of pregnant women and women with young children. This approach will ensure that codesigned solutions can engage the end‐user in healthy lifestyle practices and the solutions are sustainable.

So What?

We must shift away from a “one size fits all” approach to tailor services to respond to the differing health literacy needs of pregnant women and women with young children to support healthy lifestyle practices and reduce the NCD burden.
Death or survival, which you measure may affect conclusions: A methodological study
Authors: Shannin Jake , Brumback Babette A.
Published: October 2022

Background and Aims

Considering the opposite outcome—for example, survival instead of death—may affect conclusions about which subpopulation benefits more from a treatment or suffers more from an exposure.

Methods

For case studies on death following COVID‐19 and bankruptcy following melanoma, we compute and interpret the relative risk, odds ratio, and risk difference for different age groups. Since there is no established effect measure or outcome for either study, we redo these analyses for survival and solvency.

Results

In a case study on COVID‐19 that ignores confounding, the relative risk of death suggested that 40–49‐year‐old Mexicans with COVID‐19 suffered more from their unprepared healthcare system, using Italy's system as a baseline, than their 60–69‐year‐old counterparts. The relative risk of survival and the risk difference suggested the opposite conclusion. A similar phenomenon occurred in a case study on bankruptcy following melanoma treatment.

Conclusion

To increase transparency around this paradox, researchers reporting one outcome should note if considering the opposite outcome would yield different conclusions. When possible, researchers should also report or estimate underlying risks alongside effect measures.
Common Trends of Chiral Induced Spin Selectivity and Optical Dichroism with Varying Helix Pitch: A First‐Principles Study
Authors: Naskar Sumit , Saghatchi Aida , Mujica Vladimiro , Herrmann Carmen
Published: October 2022

Electrons ransported through a chiral molecule become spin−polarized; this phenomenon is known as chiral induced spin selectivity (CISS). It has implications for spintronics, for electrochemical and enantioselective reactions, and for electron transfer in biological systems. The CISS‐induced spin polarization in simulations and in experiment differs by orders of magnitude, and the detailed underlying mechanism is still an open question. Structure−property relationships can help elucidate this question. For this purpose, the effect of helix pitch is studied for a model helix of 20 carbon atoms for two quantities which have been found to correlate in some experiments: spin‐polarization in transmitted electrons and electronic circular dichroism (ECD). We find that even though the chirality of these model helices goes down with increased pitch, ECD and CISS go up, along with ultraviolet−visible (UV/Vis) spectra and magnetic and electric transition dipole moments. Orbital contributions to the most intense UV/Vis transition do not show a consistent qualitative picture. Tentatively, we can assign the increase in these properties to an increase of the electric polarizability with spatial extension of these helices by changing pitch.
Thermal performance of the electron transport system Complex III in seven Alabama fishes
Authors: Horne Lindsay M. , DeVries Dennis R. , Wright Russell , Irwin Elise , Staton Benjamin A. , Abdelrahman Hisham A. , Stoeckel James A.
Published: October 2022

Management of fish populations for conservation in thermally variable systems requires an understanding of the fish's underlying physiology and responses to thermal stress. Physiological research at the organismal level provides information on the overall effects of stressors such as extreme temperature fluctuations. While experiments with whole organisms provide information as to the overall effects of temperature fluctuations, biochemical assays of thermal stress provide direct results of exposure that are both sensitive and specific. Electron transport system (ETS; Complex III) assays quantify a rate‐limiting step of respiratory enzymes. Parameters that can be estimated via this approach include optimum thermal temperature (Topt) and optimal breadth of thermal performance (Tbreadth), which can both be related to organismal‐level temperature thresholds. We exposed enzymes of seven fish species (native fish chosen to represent a typical community in Alabama streams) to temperatures in the range 11–44°C. The resultant enzymatic thermal performance curves showed that Topt, the lower temperature for enzyme optimal thermal performance (Tlow), the upper temperature for enzyme optimal thermal performance (Tup), and Tbreadth differed among species. Relationships between enzymatic activity and temperature for all fish followed a pattern of steadily increasing enzyme activity to Topt before gradually decreasing with increasing temperature. A comparison of our enzyme optimum and upper‐temperature limit results versus published critical thermal maxima values supports that ETS Complex III assays may be useful for assessing organismal‐level thermal tolerance.
A hydrologic perspective of major U.S. droughts
Authors: McCabe Gregory J. , Wolock David M. , Lombard Melissa , Dudley Robert W. , Hammond John C. , Hecht Jory S. , Hodgkins Glenn A. , Olson Carolyn , Sando Roy , Simeone Caelan , Wieczorek Mike
Published: October 2022

Drought is a recurring natural hazard that has substantial human and environmental impacts. Given continued global warming and associated climate change, there is concern that droughts could become more severe and longer lasting. To better monitor and understand drought development and persistence, it is helpful to understand the development and climatic drivers of past droughts. In this study we use monthly runoff percentiles to identify five major drought events in the conterminous United States (CONUS) from 1901 through 2020. For each drought event we examined spatial patterns of departures of mean monthly precipitation, temperature, soil moisture storage, and runoff for 2,107 hydrologic units (HUs) across the CONUS. Results indicated that precipitation deficits have been the primary driver of past major‐drought events and temperature a secondary driver, even of the most recent drought event (September 1999 through September 2015) when positive temperature anomalies occurred over most of the CONUS. Additionally, negative soil moisture storage departures were more negative than runoff departures during the five drought events we examined, which emphasizes the importance of measuring both runoff and soil moisture to monitor drought conditions. We also examined the use of statistical persistence to develop short‐term (i.e., 1 month) forecasts of runoff drought conditions in the CONUS by developing autoregressive integrated moving average (ARIMA) models for each HU. Results indicated that persistence can be used to predict short‐term changes in the spatial pattern of drought and the areal extent of drought, but that predictions of runoff magnitude for any particular site are often poor.
Chiral Plasmons Enable Coherent Vortex Smith–Purcell Radiation
Authors: Zhang Zi‐Wen , Zhu Juan‐Feng , Du Chao‐Hai , Gao Fei , Han Feng‐Yuan , Liu Pu‐Kun
Published: October 2022

Recent advances in vortex Smith–Purcell radiation (V‐SPR) have spurred many breakthroughs in the generation of vortex beams for their potential applications in chiral detection, particle acceleration, communication, and imaging. However, advanced multi‐mode applications of the V‐SPR suffer from the incoherent spectrum and poor purity in producing high‐order topological charges. Here, by exploiting the rotational symmetry and Brillouin‐folding phenomenon, it is proved that the coherent V‐SPR with independently steerable high‐order topological charge is directly emitted from chiral spoof surface plasmons. Moreover, both topological charges and operation frequencies can be readily tuned, thus enabling flexible adaptability over a broad bandwidth. A proof‐of‐concept prototype is designed and fabricated in the microwave regime, in which the method is demonstrated from the perspective of symmetry and tunability. The proposed methodology can be exploited as a platform to investigate the interaction between chiral plasmons and swift electrons, promising a feasible scheme for generating coherent and tunable vortex beams from the microwave to the terahertz band.
Corrosion and degradation behavior of aluminum and copper refrigerant piping
Authors: Uchiyama Seiji , Uemura Satoshi , Hiraoka Koji , Kimura Yuji , Seki Shiro
Published: October 2022

Many types of refrigerant piping use copper alloys because of such alloys' high workability, thermal conductivity, and weatherability. However, copper is the 25th most abundant element in Earth's crust (as indicated by its Clark number: a relatively low value, ca. 0.01). Therefore, there is concern about depletion, if emerging countries and new devices such as electric vehicles use large quantities of copper. Recently, we have focused on aluminum as a lightweight metal, which is 4th place in terms of Clark number (ca. 7.6). Refrigerant piping also uses aluminum in air conditioning equipment; thus, practical applications are available. Aluminum alloys used as material for piping also contain other elements such as manganese, silicon, magnesium, copper, and iron. Regarding practical use for pipework, long‐term evaluation (more than 20 years) by corrosion is necessary. Therefore, in this study, we investigated the corrosion‐resistant characteristics of various aluminum alloys by accelerated degradation tests with changing storage conditions, such as temperature and atmosphere. In general, the corrosion of the piping materials depends on the contact atmosphere and differs between inside (refrigerant) and outside (e.g., air) piping. Specifically, there are concerns about the acid of refrigerant oils (inside piping) and corrosion by the salts in seawater (outside piping). The results from immersion tests in refrigerant and cyclic corrosion tests (intermittent cycles between salt mist and drying) proved that aluminum alloys can be used for refrigerant piping in the same way as copper materials.