bluuebunny/crossref_metadata_2025 huggingface dataset:
Patient‐Specific Self‐Powered Metamaterial Implants for Detecting Bone Healing Progress
Authors: Barri Kaveh , Zhang Qianyun , Swink Isaac , Aucie Yashar , Holmberg Kyle , Sauber Ryan , Altman Daniel T. , Cheng Boyle C. , Wang Zhong Lin , Alavi Amir H.
Published: May 2022

There is an unmet need for developing a new class of smart medical implants with novel properties and advanced functionalities. Here, the concept of “self‐aware implants” is proposed to enable the creation of a new generation of multifunctional metamaterial implantable devices capable of responding to their environment, empowering themselves, and self‐monitoring their condition. These functionalities are achieved via integrating nano energy harvesting and mechanical metamaterial design paradigms. Various aspects of the proposed concept are highlighted by developing proof‐of‐concept interbody spinal fusion cage implants with self‐sensing, self‐powering, and mechanical tunability features. Bench‐top testing is performed using synthetic biomimetic and human cadaver spine models to evaluate the electrical and mechanical performance of the developed patient‐specific metamaterial implants. The results show that the self‐aware cage implants can diagnose bone healing process using the voltage signals generated internally through their built‐in contact‐electrification mechanisms. The voltage and current generated by the implants under the axial compression forces of the spine models reach 9.2 V and 4.9 nA, respectively. The metamaterial implants can serve as triboelectric nanogenerators to empower low‐power electronics. The capacity of the proposed technology to revolutionize the landscape of implantable devices and to achieve better surgical outcomes is further discussed.
An Anode‐Free Zn–Graphite Battery
Authors: Wang Gang , Zhu Minshen , Chen Guangbo , Qu Zhe , Kohn Benjamin , Scheler Ulrich , Chu Xingyuan , Fu Yubin , Schmidt Oliver G. , Feng Xinliang
Published: May 2022

The anode‐free battery concept is proposed to pursue the aspiration of energy‐dense, rechargeable metal batteries, but this has not been achieved with dual‐ion batteries. Herein, the first anode‐free Zn–graphite battery enabled by efficient Zn plating–stripping onto a silver‐coated Cu substrate is demonstrated. The silver coating guides uniform Zn deposition without dendrite formation or side reaction over a wide range of electrolyte concentrations, enabling the construction of anode‐free Zn cells. In addition, the graphite cathode operates efficiently under reversible bis(trifluoromethanesulfonyl)imide anion (TFSI−) intercalation without anodic corrosion. An extra high‐potential TFSI− intercalation plateau is recognized at 2.75 V, contributing to the high capacity of graphite cathode. Thanks to efficient Zn plating–stripping and TFSI− intercalation–deintercalation, an anode‐free Zn–graphite dual‐ion battery that exhibits impressive cycling stability with 82% capacity retention after 1000 cycles is constructed. At the same time, a specific energy of 79 Wh kg−1 based on the mass of cathode and electrolyte is achieved, which is over two times higher than conventional Zn–graphite batteries (<30 Wh kg−1).
At their own pace: Optimal walking speed in children and adolescents
Authors: Mateos Ana , Zorrilla‐Revilla Guillermo , Rodríguez Jesús
Published: May 2022

Objectives

An important factor for human walking behavior is the speed at which an individual—adult or non‐adult—is able to move at a minimum energetic cost. Our aim was to assess the extent to which juveniles walking with adults force the group to set a pace that is energetically too costly for adults by comparing the optimal walking speed of juveniles and adults.

Materials and methods

An experimental study was carried out indoors in a sample of 74 children and adolescents of both sexes, between 7 and 14 years of age. Volunteers walked on a treadmill at six different speeds, and the gross cost of transport (CoT), minimum gross energy cost (minCoT), and optimal locomotion speed (OLS) were determined for each individual. These values were compared with the optimal values for adults, as reported in the literature.

Results

Our results show that OLS is similar in boys and girls, and that there are no sex differences in minCoT. Older individuals, as a consequence of their larger size, spend more energy at their optimal speed than younger children.

Discussion

Juveniles are not a real burden for the rest of the group in foraging societies, neither in energetic terms nor in locomotor efficiency, being able to achieve optimal walking speeds similar to adults. The so‐called energetic dilemma for sex‐mixed walking groups does not affect juveniles when moving together with adults or in sex‐mixed parties.
Metathese Reaktionen eines NHC‐stabilisierten Phosphaborens
Authors: Koner Abhishek , Morgenstern Bernd , Andrada Diego M.
Published: May 2022

Die ungesättigte BP‐Einheit stellt durch ihre neuartige Reaktivität und ihre einzigartigen physikalischen Eigenschaften eine attraktive funktionelle Gruppe dar. Nichtsdestotrotz ist ihre Anwendung begrenzt durch die sperrige Natur der B/P‐Schutzgruppen, welche erforderlich sind, um Oligomerisation zu vermeiden. Wir berichten hiermit von der Synthese und Isolation einesN‐heterozyklischen Carben‐ (NHC) stabilisierten Phosphaborens, welches eine Trimethylsilyl‐ (TMS) Funktionalität am endständigen P trägt, ein bei Raumtemperatur stabiler kristalliner Feststoff, zugänglich durch einfache NHC‐induzierte Trimethylsilylchlorid‐ (TMSCl) Eliminierung des Phosphinoboran‐Präkursors. Diese Phosphaborenverbindung, die eine genuine B=P‐Bindung enthält, zeigt die außergewöhnliche Fähigkeit, P‐zentrierte Metathese Reaktionen einzugehen, was die Isolierung einer Reihe neuartiger Phosphaborene erlaubt. Röntgenkristallographische Analyse, UV/Vis‐Spektroskopie und DFT‐Rechnungen liefern Einblicke in die B=P Bindungssituation.
Fast‐Scanning Potential‐Gated Organic Electrochemical Transistors for Highly Sensitive Sensing of Dopamine in Living Rat Brain
Authors: Li Weiqi , Jin Jing , Xiong Tianyi , Yu Ping , Mao Lanqun
Published: May 2022

Developing techniques for the highly sensitive assay of neurotransmitters is essential for understanding physiological and pathological processes. Here, we demonstrate a fast‐scanning potential (FSP)‐gated organic electrochemical transistor (OECT): for the highly sensitive sensing of dopamine (DA) in a living rat brain. The configuration combines the selectivity of fast‐scan cyclic voltammetry (FSCV) with the high sensitivity of an OECT. The combined use of FSP as a gating mode and transconductance (gm) as a sensing parameter further improve the sensing performance in terms of sensitivity, limit of detection, reproducibility, and stability. The FSP‐OECT exhibits a sensitivity of 0.899 S M−1 and a low limit of detection down to 5 nM and was validated for in vivo monitoring of the basal level and electrically stimulated release of DA.
“Like Recycles Like”: Selective Ring‐Closing Depolymerization of Poly(L‐Lactic Acid) to L‐Lactide
Authors: Cederholm Linnea , Wohlert Jakob , Olsén Peter , Hakkarainen Minna , Odelius Karin
Published: May 2022

Chemical recycling of poly(L‐lactic acid) to the cyclic monomer L‐lactide is hampered by low selectivity and by epimerization and elimination reactions, impeding its use on a large scale. The high number of side reactions originates from the high ceiling temperature (Tc) of L‐lactide, which necessitates high temperatures or multistep reactions to achieve recycling to L‐lactide. To circumvent this issue, we utilized the impact of solvent interactions on the monomer–polymer equilibrium to decrease theTcof L‐lactide. Analyzing the observedTcin different solvents in relation to their Hildebrand solubility parameter revealed a “like recycles like” relationship. The decreasedTc, obtained by selecting solvents that interact strongly with the monomer (dimethyl formamide or the green solvent γ‐valerolactone), allowed chemical recycling of high‐molecular‐weight poly(L‐lactic acid) directly to L‐lactide, within 1–4 h at 140 °C, with >95 % conversion and 98–99 % selectivity. Recycled L‐lactide was isolated and repolymerized with high control over molecular weight and dispersity, closing the polymer loop.
Regio‐ und enantioselektive, intermolekulare Aminofluorierung von Alkenen durch Iod(I)/Iod(III)‐Katalyse**
Authors: Schäfer Michael , Stünkel Timo , Daniliuc Constantin G. , Gilmour Ryan
Published: May 2022

Die regio‐ und enantioselektive, intermolekulare vicinale Fluoraminierung von α‐CF3‐Styrolen wurde durch enantioselektive II/IIII‐Katalyse erreicht. Unter Nutzung von C2‐symmetrischen, Resorcinol‐basierten Aryl Iodid‐Katalysatoren war es möglich, das kurzlebige Iodonium‐Zwischenprodukt mit einfachen Nitrilen abzufangen, die sowohl als Lösungsmittel als auch als Nucleophil fungieren. Die in situ Ritter‐Reaktion bietet direkten Zugang zu den entsprechenden Amiden (>25 Beispiele, bis zu 89 % Ausbeute und 93 : 7 e.r.). Dieses Paradigma der Hauptgruppenkatalyse kehrt die intrinsische Regioselektivität des unkatalysierten Prozesses um und bietet so einen einfachen Zugang zu tertiären, benzylischen Stereozentren, die sowohl eine CF3‐Gruppe als auch ein Fluor tragen. Es können privilegierte Phenethylamin‐Pharmakophore erzeugt werden, bei denen die vollständige lokale partielle Ladungsumkehr vorliegt (CF3δ−/Fδ− versus CH3δ+/Hδ+). Kristallographische Analysen von repräsentativen β‐Fluoramid‐Produkten zeigen Konformationen, die den stereoelektronischen Gauche‐Effekt verdeutlichen.
Ultrafast Dynamics of Photochemical Nitrile Imine Formation
Authors: Flesch Stefan , Vöhringer Peter
Published: May 2022

The chemical reactivity of nitrile imines is of great utility in organic synthesis with applications rapidly expanding into the materials and life sciences. Yet, our understanding of the electronic and molecular structures of nitrile imines remains incomplete and the elementary mechanism of their photoinduced generation is entirely unknown. Here, femtosecond infrared spectroscopy after 266 nm‐excitation of 2,5‐diphenyltetrazole has been carried out to temporally resolve the formation and structural relaxation dynamics of the nascent diphenylnitrile imine in liquid solution under ambient conditions. The infrared‐spectroscopic evolution is interpreted by an initial sequence of intersystem crossings within 250 fs followed by the cleavage of N2with formation of a structurally relaxed nitrile imine on the adiabatic ground‐state singlet surface within a few tens of picoseconds. The infrared spectrum supports the notion of a “floppy” nitrile imine molecule whose equilibrium character ranges from fully propargylic to fully allenic in the room temperature liquid solution.
Ball Milling Solid‐State Synthesis of Highly Crystalline Prussian Blue Analogue Na2−xMnFe(CN)6 Cathodes for All‐Climate Sodium‐Ion Batteries
Authors: Peng Jian , Gao Yun , Zhang Hang , Liu Zhengguang , Zhang Wang , Li Li , Qiao Yun , Yang Weishen , Wang Jiazhao , Dou Shixue , Chou Shulei
Published: May 2022

With a series of merits, Prussian blue analogs (PBAs) have been considered as superior cathode materials for sodium‐ion batteries (SIBs). Their commercialization, however, still suffers from inferior stability, considerable [Fe(CN)6] defects and interstitial water in the framework, which are related to the rapid crystal growth. Herein, a “water‐in‐salt” nanoreactor is proposed to synthesize highly crystallized PBAs with decreased defects and water, which show both superior specific capacity and rate capability in SIBs. The air‐stability, all‐climate, and full‐cell properties of our PBA have also been evaluated, and it exhibits enhanced electrochemical performance and higher volume yield than its counterpart synthesized via the water‐based co‐precipitation method. Furthermore, their highly reversible sodium‐ion storage behavior has been measured and identified via multiple in situ techniques. This work could pave the way for the PBA‐based SIBs in grid‐scale energy‐storage systems.
Sustainable synthesis of highly diastereoselective & fluorescent active spirooxindoles catalyzed by copper oxide nanoparticle immobilized on microcrystalline cellulose
Authors: Kumar Bhupender , Babu Nagendra J. , Chowhan Raju L.
Published: May 2022

Composites of copper oxide nanoparticles immobilized on microcrystalline cellulose (Cu2O@MCC) were synthesized and studied for their catalytic activity toward 1,3‐dipolar cycloaddition reaction. Azomethine ylide was in situ generated from isatin and 1,2,3,4‐tetrahydroisoquinoline (THIQ) and styrylisoxazoles/chalcones used as dipolarphiles in one‐pot synthesis of novel spiro polycyclic heterocyclic compounds. Cu2O@MCC showed excellent catalytic activity on 20 mg of composite with 30% loading of copper on MCC. The scale‐up and recyclability experiment on the 10 mmol scale revealed the sustainability of composite even after four consecutive cycles. The products were fluorescent active, obtained in good to excellent yield with high regio and diastereoselectivity. The relevant features of the developed protocol are eco‐friendly with a wide range of substrate scope and shorter reaction time.
The Wnt gene family in Tenebrio molitor and other coleopterans
Authors: Yang Lin , Li Guang‐Ya , Li Xing‐Yan , Wu Chao‐Yan , Wang Jun , Song Qi‐Sheng , Stanley David , Wei Shu‐Jun , Zhu Jia‐Ying
Published: May 2022

The Wnt gene family is involved in a wide range of developmental processes. Despite its significance, the evolution and function of Wnt genes remain largely unclear. Here, an exhaustive survey of Wnt genes was conducted in Tenebrio molitor and 17 other beetle genomes. A total of 146 Wnt genes were identified, creating a comprehensive coleopteran Wnt gene catalog. Comparative genomics indicates that dynamic evolutionary patterns of Wnt gene loss and duplication occurred in Coleoptera, leading to the diverse Wnt gene repertoire in various beetles. A striking loss of particular Wnt gene subfamilies occurs in Coleoptera. Remarkably, Wnt gene duplication was discovered for the first time in insects. Further analysis of Wnt gene expression in T. molitor indicates that each Wnt gene, including the duplicated ones, has a unique spatial or temporal expression pattern. The current study provides valuable insight into the evolution and functional validation of Wnt genes in Coleoptera.
Relativistic perihelion shift of Mercury revisited
Authors: Křížek Michal
Published: May 2022

In 1915, Albert Einstein derived a formula for an additional relativistic perihelion shift of Mercury. We give several critical comments of how this formula is treated, since the perihelion shift of Mercury is an ill‐conditioned problem. We also present various sources of nonnegligible errors, which should be taken into account.
Resonance Rayleigh scattering approach based on association complex formation with erythrosine B for determination of venlafaxine, application to the dosage form and spiked human plasma
Authors: Mohammed Bassam Shaaban , Derayea Sayed M. , Hassan Yasser F. , A. Abu‐hassan Ahmed
Published: May 2022

The interaction of venlafaxine hydrochloride (VLX) with erythrosine B was investigated using a resonance Rayleigh scattering (RRS) spectroscopic technique. In acetate buffer (pH 3.4), erythrosine B reacted with VLX to form a 1:1 ion‐pair complex with concomitant enhancement in RRS intensity that was measured at 330 nm. In addition, the stability constant and the change in free energy of the reaction were estimated. Based on this interaction a new method was developed for a sensitive VLX analysis using erythrosine B as a probe. The results indicated that this method had good selectivity in the presence of coexisting compounds. The scattering intensity (ΔIRRS) was linearly dependent on VLX concentration over the range 0.04–1.0 μg ml−1 with a determination coefficient (r) of 0.9998. The limit of detection and limit of quantitation were 0.01 and 0.03 μg ml−1, respectively. This method could be suitably used for analysis of VLX in pharmaceutical capsules and human plasma.
Carboxylative efficacy of trans and cisMK7 and comparison with other vitamin K isomers
Authors: Cirilli Ilenia , Orlando Patrick , Silvestri Sonia , Marcheggiani Fabio , Dludla Phiwayinkosi V. , Kaesler Nadine , Tiano Luca
Published: May 2022

Carboxylative enzymes are involved in many pathways and their regulation plays a crucial role in many of these pathways. In particular, γ‐glutamylcarboxylase (GGCX) converts glutamate residues (Glu) into γ‐carboxyglutamate (Gla) of the vitamin K‐dependent proteins (VKDPs) activating them. VKDPs include at least 17 proteins involved in processes such as blood coagulation, blood vessels calcification, and bone mineralization. VKDPs are activated by the reduced form of vitamin K, naturally occurring as vitamin K1 (phylloquinone) and K2 (menaquinones, MKs). Among these, MK7 is the most efficient in terms of bioavailability and biological effect. Similarly to other trans isomers, it is produced by natural fermentation or chemically in both trans and cis. However, the efficacy of the biological effect of the different isomers and the impact on humans are unknown. Our study assessed carboxylative efficacy of trans and cis MK7 and compared it with other vitamin K isomers, evaluating both the expression of residues of carboxylated Gla‐protein by western blot analysis and using a cell‐free system to determine the GGCX activity by HPLC. Trans MK7H2 showed a higher ability to carboxylate the 70 KDa GLA‐protein, previously inhibited in vitro by warfarin treatment. However, cis MK7 also induced a carboxylation activity albeit of a small extent. The data were confirmed chromatographically, in which a slight carboxylative activity of cis MK7H2 was demonstrated, comparable with both K1H2 and oxidized trans MK7 but less than trans MK7H2. For the first time, a difference of biological activity between cis and trans configuration of menaquinone‐7 has been reported.
An injectable gelatin/sericin hydrogel loaded with human umbilical cord mesenchymal stem cells for the treatment of uterine injury
Authors: Chen Lixuan , Li Ling , Mo Qinglin , Zhang Xiaomin , Chen Chaolin , Wu Yingnan , Zeng Xiaoli , Deng Kaixian , Liu Nanbo , Zhu Ping , Liu Mingxing , Xiao Yang
Published: May 2022

Abnormal endometrial receptivity is a major cause of the failure of embryo transplantation, which may lead to infertility, adverse pregnancy, and neonatal outcomes. While hormonal treatment has dramatically improved the fertility outcomes in women with endometriosis, a substantial unmet need persists in the treatment. In this study, methacrylate gelatin (GelMA) and methacrylate sericin (SerMA) hydrogel with human umbilical cord mesenchymal stem cells (HUMSC) encapsulation was designed for facilitating endometrial regeneration and fertility restoration through in situ injection. The presented GelMA/10%SerMA hydrogel showed appropriate swelling ratio, good mechanical properties, and degradation stability. In vitro cell experiments showed that the prepared hydrogels had excellent biocompatibility and cell encapsulation ability of HUMSC. Further in vivo experiments demonstrated that GelMA/SerMA@HUMSC hydrogel could increase the thickness of endometrium and improve the endometrial interstitial fibrosis. Moreover, regenerated endometrial tissue was more receptive to transfer embryos. Summary, we believed that GelMA/SerMA@HUMSC hydrogel will hold tremendous promise to repair or regenerate damaged endometrium.
First experiences of integrating computational thinking into a blended learning in‐service training program for STEM teachers
Authors: Knie Lisa , Standl Bernhard , Schwarzer Stefan
Published: May 2022

Over the last two decades, computational thinking (CT) has gained importance in discussions about competencies that students require to deal with complex problems in a world shaped by digitalization. Therefore, schools and teachers should integrate CT into their instructional practices. Particularly, the STEM (Science, Technology, Engineering, and Mathematics) subjects are seen as a meaningful context for embedding CT. Yet, there are only a few professional development programs that address STEM teachers and how to integrate CT. Thus, in our study, we redesigned an in‐service teacher training program. The redesigned program was offered in a blended‐learning format, consisting of alternating digital and face‐to‐face phases. As part of the digital phases, an interactive online self‐learning module on CT was introduced to foster transdisciplinary competencies in the field of STEM to solve complex problems. To identify the perceptions and development of the participants of the training program and the online module on CT a within‐subject design was used with a questionnaire survey, conducted with a pre‐post‐follow‐up design. The first results of the ongoing survey indicate high satisfaction with both the program itself and the online CT module. At the beginning of the program, about two‐thirds of the participating teachers were completely unfamiliar with the term CT, nevertheless, interest in the new topic was high. It was shown the program was able to create initial awareness of the meaning and importance of CT. In addition, teachers who have engaged with CT during the intervention seem to use CT‐related practices more often in the classroom afterward.
Genetic Survey of Psilocybe Natural Products
Authors: Dörner Sebastian , Rogge Kai , Fricke Janis , Schäfer Tim , Wurlitzer Jacob M. , Gressler Markus , Pham Duyen N. K. , Manke David R. , Chadeayne Andrew R. , Hoffmeister Dirk
Published: May 2022

Psilocybe magic mushrooms are best known for their main natural product, psilocybin, and its dephosphorylated congener, the psychedelic metabolite psilocin. Beyond tryptamines, the secondary metabolome of these fungi is poorly understood. The genomes of five species (P. azurescens, P. cubensis, P. cyanescens, P. mexicana, and P. serbica) were browsed to understand more profoundly common and species‐specific metabolic capacities. The genomic analyses revealed a much greater and yet unexplored metabolic diversity than evident from parallel chemical analyses. P. cyanescens and P. mexicana were identified as aeruginascin producers. Lumichrome and verpacamide A were also detected as Psilocybe metabolites. The observations concerning the potential secondary metabolome of this fungal genus support pharmacological and toxicological efforts to find a rational basis for yet elusive phenomena, such as paralytic effects, attributed to consumption of some magic mushrooms.
T‐Joint Micromixer Coupled with Deforming Diaphragm
Authors: Madapati Nikhilesh , Arumuru Venugopal
Published: May 2022

A novel active micromixer design involving an oscillating diaphragm is proposed. A simulation study is performed to determine the effect of diaphragm length, amplitude, and frequency of the oscillating diaphragm on the mixing index. The geometry is a simple T‐joint with an elongated channel for the outlet with a diaphragm on the outlet channel wall. The fluids at the inlets are similar in fluid properties with the same flow rate and diffusion constant. The mixing index saturates with increasing frequency and amplitude of oscillation for a given diaphragm length. The diaphragm's effectiveness was calculated based on the pressure difference between the diaphragm inlet and outlet zone. The effectiveness declined with an increase in the frequency of the diaphragm oscillation. An analytical expression is derived to find the effect of the frequency and amplitude of the diaphragm oscillation on the mixing index. This simple novel design may find wide applications in various industrial fields.
Nature‐inspired materials and designs for flexible lithium‐ion batteries
Authors: Li Heng , Wang Huibo , Chan Dan , Xu Zhu , Wang Kexuan , Ge Mingzheng , Zhang Yanyan , Chen Shi , Tang Yuxin
Published: May 2022

Flexible lithium‐ion batteries (FLBs) are of critical importance to the seamless power supply of flexible and wearable electronic devices. However, the simultaneous acquirements of mechanical deformability and high energy density remain a major challenge for FLBs. Through billions of years of evolutions, many plants and animals have developed unique compositional and structural characteristics, which enable them to have both high mechanical deformability and robustness to cope with the complex and stressful environment. Inspired by nature, many new materials and designs emerge recently to achieve mechanically flexible and high storage capacity of lithium‐ion batteries at the same time. Here, we summarize these novel FLBs inspired by natural and biological materials and designs. We first give a brief introduction to the fundamentals and challenges of FLBs. Then, we highlight the latest achievements based on nature inspiration, including fiber‐shaped FLBs, origami and kirigami‐derived FLBs, and the nature‐inspired structural designs in FLBs. Finally, we discuss the current status, remaining challenges, and future opportunities for the development of FLBs. This concise yet focused review highlights current inspirations in FLBs and wishes to broaden our view of FLB materials and designs, which can be directly “borrowed” from nature.
Facile carbon cloth activation strategy to boost oxygen reduction reaction performance for flexible zinc‐air battery application
Authors: Manjunatha Revanasiddappa , Yuan Jingchao , Hongwei Li , Deng Shu‐Qi , Ezeigwe Ejikeme R. , Zuo Yinze , Dong Li , Li Aijun , Yan Wei , Zhang Fangzhou , Zhang Jiujun
Published: May 2022

Flexible and all‐solid‐state zinc‐air batteries (ZABs) are highly useful and also in demand due to their theoretical high energy densities and special applications. The limitation in their performance arises due to their catalyst‐coated cathode electrodes in terms of catalytic activity and stability as well as cost. In this paper, a novel and environmentally friendly activation strategy is developed to activate the carbon cloth (CC) for the electrodes. The activated CC serves as a catalyst‐free air cathode with high conductivity, excellent mechanical strength, and flexibility, in addition to low cost. The strategy is performed by simply electro‐oxidizing and electroreducing CC under ultrahigh direct current (DC) voltage in a diluted NH4Cl aqueous electrolyte. It is found that the electro‐oxidation not only results in the formation of a graphene‐like exfoliated carbon layer on the surface of CC but also induces the incorporation of oxygen‐containing groups and doping of nitrogen and chloride atoms. After the electroreduction, the π‐conjugated carbon network of CC is partially restored, leading to the recovery of electroconductivity. Such an electroactivated CC shows excellent oxygen reduction reaction activity. The aqueous flexibility and all‐solid‐state ZABs are assembled using such an electroactivated CC cathode without any catalyst loading. Both ZABs can achieve good durability and deliver high peak power density and an energy density as high as 690 Wh kg−1, demonstrating the excellent potential of this electroactivated CC in practical devices.
Recent advances in solar‐driven CO2 reduction over g‐C3N4‐based photocatalysts
Authors: Xu Quanlong , Xia Zhihua , Zhang Jingmei , Wei Zhiyi , Guo Qin , Jin Huile , Tang Hua , Li Shouzhu , Pan Xuecong , Su Zhi , Wang Shun
Published: May 2022

The persistent increase of CO2 levels in the atmosphere, already exceeding 400 ppm, urges the exploration of CO2 emission reduction and recycling technologies. Ideally, photocatalytic conversion of CO2 into valuable hydrocarbons realizes solar‐to‐chemical energy conversion, which is a desirable “kill two birds with one stone” strategy; namely, CO2 photoreduction can simultaneously tackle energy shortage and keep global carbon balance. Graphitic carbon nitride (g‐C3N4) working on CO2 reduction reaction deserves a highlight not only for the metal‐free feature that endows it with low cost, tunable electronic structure, and easy fabrication properties but also because of its strong reduction ability. The present review concisely summarizes the latest advances of g‐C3N4‐based photocatalysts toward CO2 reduction. It starts with the discussion of thermodynamics and dynamics aspects of the CO2 reduction process. Then the modification strategies to promote g‐C3N4‐based photocatalysts in CO2 photoreduction have been discussed in detail, including surface functionalization, molecule structure engineering, crystallization, morphology engineering, loading cocatalyst, and constructing heterojunction. Meanwhile, the intrinsic factors affecting CO2 reduction activity and selectivity are analyzed and summarized. In the end, the challenges and prospects for the future development of highly g‐C3N4‐based photocatalysts in CO2 reduction are also presented.
Stretchable supercapacitor based on a hierarchical PPy/CNT electrode and hybrid hydrogel electrolyte with a wide operating temperature
Authors: Ren Yanfang , Liu Yunlong , Wang Siying , Wang Qian , Li Shuhong , Wang Wenjun , Dong Xiaochen
Published: May 2022

Hydrogel is frequently used as a solid electrolyte for all solid‐state supercapacitors (SCs) because of its liquid‐like ion‐transport property and high conformability. However, due to the higher water content, the hydrogel electrolyte undergoes inevitable freezing and/or dehydration with climate change. Herein, polypyrrole/carbon all‐solid‐state SCs (PCSCs) were developed based on a hierarchical polypyrrole/carbon nanotube electrode and a highly stretchable double‐network polymer hydrogel electrolyte with LiCl/ethylene glycol as a mixed solvent. The PCSCs showed excellent electrochemical performance and cycle stability with a wide operating temperature. The specific capacitances could reach 202.2 and 112.3 mF cm−2 at current densities of 0.5 and 3.0 mA cm−2, respectively. Meanwhile, the PCSCs showed outstanding mechanical properties in maintaining a high areal capacitance under deformations of bending and tension. The excellent water retention of the device also ensured the stable electrochemical performance of PCSCs in a wide temperature range (30–80°C), which could potentially represent a reliable application in various harsh environments.
Assembly ofϵ‐Keggin Polyoxometalate from Molecular Crystal to Zeolitic Octahedral Metal Oxide
Authors: Wang Jie , Li Denan , Yang Honggui , Yao Shufan , Zhu Qianqian , Sadakane Masahiro , Li Yanshuo , Ueda Wataru , Zhang Zhenxin
Published: May 2022

Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. Newϵ‐Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized.31P NMR spectroscopy shows that reduction of MoVI‐based molybdates forms anϵ‐Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than theϵ‐Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na+is used as the adsorbent, which effectively separates C2hydrocarbon mixtures.
Ultra‐Long Lived Luminescent Triplet Excited States in Cyclic (Alkyl)(amino)carbene Complexes of Zn(II) Halides
Authors: Mrózek Ondřej , Gernert Markus , Belyaev Andrey , Mitra Mousree , Janiak Lars , Marian Christel M. , Steffen Andreas
Published: May 2022

The high element abundance and d10 electron configuration make ZnII‐based compounds attractive candidates for the development of novel photoactive molecules. Although a large library of purely fluorescent compounds exists, emission involving triplet excited states is a rare phenomenon for zinc complexes. We have investigated the photophysical and ‐chemical properties of a series of dimeric and monomeric ZnII halide complexes bearing a cyclic (alkyl)(amino)carbene (cAAC) as chromophore unit. Specifically, [(cAAC)XZn(μ‐X)2ZnX(cAAC)] (X=Cl (1), Br (2), I (3)) and [ZnX2(cAAC)(NCMe)] (X=Br (4), I (5)) were isolated and fully characterized, showing intense visible light photoluminescence under UV irradiation at 297 K and fast photo‐induced transformation. At 77 K, the compounds exhibit improved stability allowing to record ultra‐long lifetimes in the millisecond regime. DFT/MRCI calculations confirm that the emission stems from 3XCT/LEcAAC states and indicate the phototransformation to be related to asymmetric distortion of the complexes by cAAC ligand rotation. This study enhances our understanding of the excited state properties for future development and application of new classes of ZnII phosphorescent complexes.
Ergochaeglobosins A—E, Unprecedented Heterodimers of Cytochalasan and Ergosterol fromChaeglobosin globosumP2‐2‐2
Authors: Peng Xiaogang , Liu Junjun , Qin Chunlun , Wu Qian , Li Wanpeng , Mohammadipanah Fatemeh , Ruan Hanli
Published: May 2022

Comprehensive Summary

Five novel heterodimers of cytochalasan and ergosterol, ergochaeglobosins A—E, were isolated from an endophytic fungusChaetomium globosumP2‐2‐2. Ergochaeglobosin A (1) possesses an unprecedented 5/6/13/6/5/6/6/6 fused octacyclic ring system, and ergochaeglobosins B (2) and C (3) form a unique 5/6/13/6/6/6/6/5 fused octacyclic ring system, whereas ergochaeglobosins D (4) and F (5) are the first cytochalasan heterodimers formedviaa N‐1′/C‐3′′ single bond. Their structures with absolute configurations were established by extensive spectroscopic analyses, single‐crystal X‐ray diffraction, and ECD calculations. The plausible biogenetic pathway of 1—5 was postulated. Compound 1 exhibited inhibitory effects against ConA‐induced T cells and LPS‐induced B cells proliferation with IC50values of 19.2 and 14.1 μmol/L, respectively. Co‐treatment of 3 (20 μmol/L) with TRAIL (150 ng/mL) could significantly decrease the cell viability of A549 by 24.9% comparing with monotherapy of 3 (20 μmol/L).
A varying‐radius cable equation for the modelling of impulse propagation in excitable fibres
Authors: Alqahtani Abdulrahman , Alabed Amr , Alharbi Yousef , Bakouri Mohsen , Lovell Nigel H. , Dokos Socrates
Published: May 2022

In this study, we present a varying‐radius cable equation for nerve fibres taking into account the varying diameter along the neuronal segments. Finite element neuronal models utilising the classical (fixed‐radius) and varying‐radius cable formulations were compared using simple and realistic morphologies under intra‐ and extracellular electrical stimulation protocols. We found that the use of the classical cable equation to model intracellular neural electrical stimulation exhibited an error of 17% in a passive resistive cable model with abrupt change in radius from 1 to 2 μm, when compared to the known analytical solution and varying‐radius cable formulation. This error was observed to increase substantially using more realistic neuron morphologies and branching structures. In the case of extracellular stimulation however, the difference between the classical and varying‐radius formulations was less pronounced, but we expect this difference will increase under more complex stimulation paradigms such as high‐frequency stimulation. We conclude that for computational neuroscience applications, it is essential to use the varying‐radius cable equation for accurate prediction of neuronal responses under electrical stimulation.
Mean control chart based on ranked set schemes for unknown skewed probability distribution and parameters
Authors: Riaz Muhammad , Mehmood Rashid , Rehman Masooda , Ali Iftikhar , Zaman Babar
Published: May 2022

Several structures of mean control chart based on ranked set schemes are available in literature. These structures involve assumptions, that is, process distribution is known and sufficient amount of samples is available in estimating unknown parameters. It is a fact that the restricted assumptions do not fulfill in several processes. In such situation, the actual false alarm rate of mean control chart under ranked set schemes is deviated from true level. This issue has taken as one of the motivations of present study. In this study, we have designed a skewness correction mean control chart for managing the situations where skewed probability distribution and process parameters are unknown. The proposed skewness correction mean control chart depends on known skewness level of a process characteristics rather than the restricted assumption of known probability distribution. Furthermore, proposed skewness correction and usual mean control charts are assessed using actual false alarm rate. The outcomes revealed that actual false alarm rate of proposed skewness correction mean control chart remains close to true level when assumption(s) is violated compared to usual mean control chart. To explain the implementation procedure as well as advantages of the proposed control chart over usual, simulated and real data examples are considered. The real data example from agriculture field is included in which proposed control chart is implemented to monitor calcium + magnesium contents of irrigation water.
A Vanadium Dioxide‐PMMA Composite For Microwave Radiation Switching
Authors: Kucheriv Olesia I. , Grygoruk Valery I. , Oliynyk Viktor V. , Zagorodnii Volodymyr V. , Launets Vilen L. , Rotaru Aurelian , Gural'skiy Il'ya A.
Published: May 2022

Reconfigurable radio‐frequency components are in high demand for modern communication systems as they can be involved in multiband and multistandard electronic devices. The key part of such components is an active switching element. This work offers a way to obtain an efficient microwave switch using vanadium dioxide‐poly (methyl methacrylate) composite. Differential scanning calorimetry, SQUID magnetometery, and impedance spectroscopy measurements were used to characterize the phase transition in the proposed composite. Temperature induced metal‐insulator transition occurs at technologically attractive 341 K. The transition leads to a change of microwave transmission trough VO2‐PMMA composite from −4.9 dB for low‐temperature monoclinic form to −5.8 dB for high‐temperature rutile form. This provides an ability to tune the material's transparency in the microwave range, while the shaping polymer matrix provides the proper mechanical processability of the switching element.
Cytologic manifestations of Hodgkin lymphoma in serous effusions
Authors: AbdullGaffar Badr , Raman Lakshmiah
Published: May 2022

Serous effusions occur in a small group of patients with classic Hodgkin lymphoma (cHL). Most effusions are benign inflammatory fluids. Malignant effusions predominantly in patients with treated relapsed diseases or rarely as a primary manifestation are diagnostically challenging to cytopathologists. Established cases of cHL with effusions were retrieved. Cytology slides were screened looking for Reed–Sternberg–Hodgkin (RSH) cells and patterns of background inflammatory cells. Cellblocks and their corresponding immunocytochemistry (ICC) slides were examined. The cytologic findings were correlated with nodal biopsy histopathologic and immunohistochemical features. We found six cases of benign and malignant pleural and pericardial effusions in patients with mediastinal nodular sclerosis‐type cHL. Various cytomorphologic patterns were observed. Slides revealed sparsely scattered either isolated or aggregated mononuclear, binucleated and multinucleated RSH‐like cells. Some may have been either disregarded as reactive mesothelial or histiocytic cells, or confused with other RSH‐like malignant cells. The background varied between characteristic mixed inflammatory milieu, predominantly small lymphocytic or lymphohistiocytic with or without reactive mesothelial cells. Cytologic examination showed three positive cases (two cases with RSH cells confirmed by cellblock section ICC, one case with a mixed inflammatory infiltrate), and three benign effusions (one case with atypical RSH‐like reactive mesothelial cells confirmed by ICC). Effusions associated with cHL exhibit different cytologic patterns. A high level of vigilance with utility of ICC has an important role in suspecting primary cases and confirming recurrences in known cases. The various cytologic patterns of cHL‐associated benign and malignant effusions might reflect parallel pathophysiologic mechanisms.
Cytomorphology of nodular histiocytic/mesothelial hyperplasia
Authors: Jin Xiaobing , Jing Xin , McHugh Jonathan B. , Pantanowitz Liron
Published: May 2022

Nodular histiocytic/mesothelial hyperplasia (NHMH) is a pathologic entity that has not been well characterized in the cytopathology literature. This is unfortunate because if unrecognized, NHMH may be misdiagnosed when encountered in cytology specimens. The aim of this communication is to accordingly alert cytologists about NHMH by means of an illustrative case report.
Bulky HybridC‐Scorpionate/Amidinate Complexes of Lithium and Zinc
Authors: Mandel Miles J. , Krieck Sven , Görls Helmar , Westerhausen Matthias
Published: May 2022

Lithiation of the bis(pyrazolyl)methanes H2C(PzAd,Me)2(1 a) and H2C(PzPh,Ph)2(1 b) and subsequent addition ofN,N’‐diisopropylcarbodiimide in THF yields [(thf)Li{(PzAd,Me)2HC−C(=NiPr)(NiPr)}] (2 a) and [(thf)Li{(PzPh,Ph)2HC−C(=NiPr)(NiPr)}] (2 b). For comparison reasons, the structure of [(thf)Li{(PztBu,tBu)2HC−C(=NCy)(NCy)}] (I) has been determined as well. Protolysis with aqueous ammonium chloride solution gives (PzAd,Me)2HC−C(=NiPr)(NHiPr) (3 a) and (PzPh,Ph)2HC−C(=NiPr)(NHiPr) (3 b). Zincation with diethylzinc leads to the formation of [EtZn{(PzAd,Me)2HC−C(=NiPr)(NiPr)}] (4 a) and [EtZn{(PzPh,Ph)2HC−C(=NiPr)(NiPr)}] (4 b). The metathetical approach allows preparation and isolation of [ClZn{(PzPh,Ph)2HC−C(=NiPr)(NiPr)}] (5). A comparison of the molecular structures of the lithium and zinc complexes allows to elucidate the influence of electronegativity on structural parameters because tetra‐coordinate Li and Zn ions have very similar radii.
Humins‐Like Solid Support for Palladium Immobilization: Highly Efficient and Recyclable Catalyst for Cross‐Coupling Reactions
Authors: Galaverna Renan S. , Fernandes Lucas P. , Menezes da Silva Vitor H. , de Siervo Abner , Pastre Julio C.
Published: May 2022

In the present work, a new humins‐like resin was prepared using 2,5‐bis(hydroxymethyl)furan (DHMF) and maleic anhydride in 2 min at 110 °C. Such a new material was used as a solid support for palladium immobilization. For metal anchoring, encapsulation was the method of choice and palladium was encapsulated byin‐situpolymerization. This resulting Pd@DHMF‐based catalyst was characterized by solid‐state13C NMR, FT‐IR, SEM, TGA, DSC, XRD, and XPS. To demonstrate proof of concept, Heck and Suzuki cross‐coupling reactions were selected to evaluate the activity and reusability of the catalyst. Green solvents such asγ‐valerolactone (GVL), CyreneTMand ethylene carbonate proved to be excellent reaction media for Heck coupling, whereas EtOH/H2O was preferred for Suzuki coupling. Yields of up to 99 % were obtained in both cases. The recyclability of the Pd@DHMF‐based catalyst was also demonstrated, 7 cycles have been achieved without loss of catalytic activity in both Heck and Suzuki reactions.
Competitive Host‐guest Electrochemical Detection of Ivermectin Drug Using a β‐Cyclodextrin/Graphene‐based Electrode
Authors: Silva Martin K. L. , Simões Rafael P. , Leão Alcides L. , Lapa Rainer M. L. , Rascón Jesús , Cesarino Ivana
Published: May 2022

The present study describes the novel development and application of an ivermectin (IVM) sensing electrochemical platform based on reduced graphene oxide (rGO) and the macrocyclic host β‐cyclodextrin (β‐CD) molecule. The sensing method was based in the host‐guest characteristics of β‐CD and competitive interaction between the target analyte and the methylene blue (MB) redox probe. Differential pulse voltammetry (DPV) was employed for the detection of IVM and a linear response between 0.5 and 40.0 μmol L−1with a limit of detection of 0.25 μmol L−1was obtained using the glassy carbon (GC)/rGO/β‐CD electrode. The sensing platform was successfully applied for the detection of IVM in tap water samples, which may expand the applications of β‐CD towards the analysis of other chemical species.
Ultra‐small Size ZIF‐8 Materials for Efficient and Selective Electrocatalytic Reduction of CO2 to CO
Authors: Zhou Liangyin , Li Hongji , Wang Dandan , Jiang Wei , Wu Yuanyuan , Shang Liaofang , Guo Chunyi , Liu Chunbo , Ren Baixiang
Published: May 2022

Zeolitic Imidazolate Frameworks (ZIFs) are considered as a novel porous material combining high stability in inorganic zeolites with high porosity and organic functionality of MOFs. The cage‐like structure selectively and efficiently traps CO2, which is an indispensable and critical step for Electrocatalytic CO2 Reduction Reaction (CO2RR). In this work, ultrasmall ZIF‐8 nanomaterials are synthesized by tuning the molar ratio of the feedstock and used as electrocatalysts for the selective reduction of CO2 to CO. The catalytic activity of the ultra‐small size ZIF‐8 material for the electrocatalytic reduction of CO2 can reach satisfactory results with a Faraday efficiency of 91 % for CO and a stability of 12.5 h at a high applied potential of −1.8 V vs. RHE. The investigation can provide a new idea to explore for the design and improvement of catalysts for CO2RR.
Two‐phase adaptive cluster sampling with circular field plots
Authors: Prentius Wilmer , Grafström Anton
Published: May 2022

Adaptive cluster sampling (ACS) is extended to the case when the primary sampling units consist of circular field plots. When conducting field work for environmental monitoring, circular field plots are often preferred as they are easily set up by field workers. ACS was developed by tessellating the area frame into square plots. By using a two‐phase sampling procedure, a first‐phase sample of circular field plots can be established as the primary sampling units, from which ACS can be performed. However, the two‐phase approach introduces some additional complexity in estimation. We derive estimators and conservative variance estimators for two‐phase ACS using circular field plots. For some populations, ACS may produce a highly variable sample size. To deal with this issue, we provide a way to reduce the maximal possible sample size. By using simulated populations, we compare the efficiencies of two‐phase methods with ordinary simple random sampling. The simulations show that the two‐phase approach is a competitive alternative to regular ACS, and that adding a restriction to the maximal possible sample size makes ACS a viable alternative for a larger set of populations.
Low lattice thermal conductivity of hydride‐based cubic antiperovskites A3HB (a = Li, Na; B = S, se, Te) with higher‐order anharmonicity correction
Authors: Xiao Yanan , Sui Pengfei , Zhao Yinchang , Ni Jun , Meng Sheng , Dai Zhenhong
Published: May 2022

Quartic anharmonicity is of vital significance in accurately determining thermal conductivity (κL). Here, using first‐principles calculation method combined with Boltzmann transport equation (BTE), compressive sensing techniques and self‐consistent phonon (SCP) theory, we investigate the heat transport properties of five hydride‐based cubic antiperovskites A3HB (A = Li, Na; B = S, Se, Te) with the inclusion of scattering rates and phonon frequency shifts induced by quartic anharmonicity, which do not contain orthorhombic Na3HS. It is worth noting that only the values of κL obtained by SCP theory are valid for Li3HS and Na3HS, because there is imaginary frequency in HA phonon mode, which makes the conventional calculation of BTE invalid. We also find that quartic anharmonicity is important to capture the reasonable temperature dependence of the κL, while only taking phonon frequency shifts (4 ph scattering processes) into account will result in weaker (stronger) temperature dependence. The calculated κL based SCP theory exhibits a remarkably low value at 300 K, which indicates that the cubic antiperovskites A3HB (A = Li, Na; B = S, Se, Te) are potential thermoelectric materials.