bluuebunny/crossref_metadata_2025 huggingface dataset:
Non‐Stationary Complementary Non‐Uniform Sampling (NOSCO NUS) for Fast Acquisition of Serial 2D NMR Titration Data
Authors: Romero Javier A. , Nawrocka Ewa K. , Shchukina Alexandra , Blanco Francisco J. , Diercks Tammo , Kazimierczuk Krzysztof
Published: September 2020

NMR spectroscopy offers unique benefits for ligand binding studies on isotopically labelled target proteins. These benefits include atomic resolution, direct distinction of binding sites and modes, a lowest detectable affinity limit, and function independent setup. Yet, retracing protein signal assignments from apo to holo states to derive exact dissociation constants and chemical shift perturbation amplitudes (for ligand docking and structure‐based optimization) requires lengthy titration series of 2D heteronuclear correlation spectra at variable ligand concentration that may exceed the protein's lifetime and available spectrometer time. We present a novel method to overcome this critical limitation, based on non‐stationary complementary non‐uniform sampling (NOSCO NUS) combined with a robust particle swarm optimization algorithm. We illustrate its potential in two challenging studies with very distinct protein sizes and binding affinities, showing that NOSCO NUS can reduce measurement times by an order of magnitude to make such highly informative NMR titration studies more broadly feasible.
Design of a Single‐Atom Indiumδ+–N4Interface for Efficient Electroreduction of CO2to Formate
Authors: Shang Huishan , Wang Tao , Pei Jiajing , Jiang Zhuoli , Zhou Danni , Wang Yu , Li Haijing , Dong Juncai , Zhuang Zhongbin , Chen Wenxing , Wang Dingsheng , Zhang Jiatao , Li Yadong
Published: September 2020

Main‐group element indium (In) is a promising electrocatalyst which triggers CO2reduction to formate, while the high overpotential and low Faradaic efficiency (FE) hinder its practical application. Herein, we rationally design a new In single‐atom catalyst containing exclusive isolated Inδ+–N4atomic interface sites for CO2electroreduction to formate with high efficiency. This catalyst exhibits an extremely large turnover frequency (TOF) up to 12500 h−1at −0.95 V versus the reversible hydrogen electrode (RHE), with a FE for formate of 96 % and current density of 8.87 mA cm−2at low potential of −0.65 V versus RHE. Our findings present a feasible strategy for the accurate regulation of main‐group indium catalysts for CO2reduction at atomic scale.
A New Mechanically‐Interlocked [Pd2L4] Cage Motif by Dimerization of two Peptide‐based Lemniscates
Authors: Schulte Thorben R. , Holstein Julian J. , Schneider Laura , Adam Abdulselam , Haberhauer Gebhard , Clever Guido H.
Published: September 2020

Most metallo‐supramolecular assemblies of low nuclearity adopt simple topologies, with bridging ligands spanning neighboring metal centers in a direct fashion. Here we contribute a new structural motif to the family of host compounds with low metal count (two) that consists of a pair of doubly‐interlocked, Figure‐eight‐shaped subunits, also termed “lemniscates”. Each metal is chelated by two chiral bidentate ligands, composed of a peptidic macrocycle that resembles a natural product with two pyridyl‐terminated arms. DFT calculation results suggest that dimerization of the mononuclear halves is driven by a combination of 1) Coulomb interaction with a central anion, 2) π‐stacking between intertwined ligand arms and 3) dispersive interactions between the structure's compact inner core bedded into an outer shell composed of the cavitand‐type macrocycles. The resulting cage‐like architecture was characterized by NMR, MS and X‐ray structure analyses. This new mechanically bonded system highlights the scope of structural variety accessible in metal‐mediated self‐assemblies composed of only a few constituents.
Palladium‐catalyzed cross‐coupling reactions of coumarin derivatives: An overview
Authors: Kanchana U.S. , Diana Elizabeth J. , Mathew Thomas V. , Anilkumar Gopinathan
Published: September 2020

Coumarins are omnipresent in several plants and exhibit a plethora of pharmacological properties, making them an important scaffold in organic synthesis. Naturally, the chemistry of this motif has attracted ever‐increasing attention, among which palladium‐catalyzed coupling reactions are the most prevalent one. Numerous useful, easy, and concise syntheses and reactions have been achieved using palladium‐catalyzed coupling reactions. This review focuses on recent advances in palladium‐catalyzed cross‐coupling reactions such as Suzuki, Heck, Stille, Sonogoshira etc. reactions of coumarin derivatives and covers the literature from 2001 to 2020.
Covalent surface functionalization of nonwoven fabrics with controlled hydrophobicity, water absorption, and pH regulation properties
Authors: Dan Yoav , Buzhor Marina , Raichman Daniel , Menashe Eti , Rachmani Oren , Amir Elizabeth
Published: September 2020

A modular method for functionalization of nonwoven fabrics was developed using a two‐step process. In the first step, the fabrics were grafted with a linker molecule, 10‐undecenoyl chloride, via esterification, followed by attachment of a functional material under UV irradiation. Perfluorodecanethiol and 3‐mercaptopropionic acid (MPA) were connected to the linker‐modified fabrics using thiol‐ene click chemistry. Perfluorodecanethiol modified fabrics exhibited hydrophobicity with water contact angle of about 140° while MPA‐modified fabrics were able to lower the pH of a solution by about 1.6. We additionally demonstrated the possibility to connect functional polymers to the linker‐modified fabrics by radical graft polymerization of acrylic acid; this produced a thin layer of the polymer on the surface of the fabric. Fabrics modified with poly(acrylic acid) exhibited increased hydrophilicity with water contact angle of 0° for both cotton and viscose‐polyester fabrics, while the water absorption capability for polypropylene fabrics increased from about 50 to 1200%.
2020 Roadmap on Zinc Metal Batteries
Authors: Xu Chenxuan , Zhang Yu , Zhang Naiqing , Liu Xiaoyu , Yi Jin , Liu Xiaoqing , Lu Xihong , Ru Qiang , Lu Hao , Peng Xinwen , Zhao X. S. , Ma Jianmin
Published: September 2020

Metallic zinc (Zn) is considered to be a safe and low‐cost anode for rechargeable batteries. Thus, several zinc metal batteries (ZMBs) have been well developed, i. e., zinc silver batteries, Zn−MnO2 batteries, nickel‐zinc batteries, zinc‐air batteries and other kinds of zinc ion batteries. ZMBs are strongly correlated with electrochemistry, electrodes, electrolytes and battery structures. To support the development of this field, we herein invite some famous research experts to write this roadmap for giving some guidance in future research. The roadmap will include their research status, challenge, opportunities, and the technology advance in their fields. We expect this roadmap will produce active influence in developing green, low‐cost, safe ZMBs for our bright life in future.
Folic acid antagonist use before and during pregnancy and risk for selected birth defects
Authors: Kerr Stephen M. , Parker Samantha E. , Mitchell Allen A. , Tinker Sarah C. , Werler Martha M.
Published: September 2020

Background

Maternal folic acid (FA) intake before and during early pregnancy reduces the risk for neural tube defects (NTDs); evidence suggests it may also reduce the risk for oral clefts, urinary defects, and cardiac defects. We sought to re‐examine the use of drugs, which affect folate metabolism, dihydrofolate reductase inhibiting (DHFRI) medications, and anti‐epileptic drugs (AEDs), in data collected in the post‐FA fortification era (1998+) in the Slone Birth Defects Study.

Methods

We assessed maternal DHFRI and AED use and risk for NTDs, oral clefts, and urinary and cardiac defects. We estimated odds ratios (ORs) and 95% confidence intervals (CIs) using logistic regression. We assessed daily average FA intake of ≥400 mcg as a potential effect modifier.

Results

We analyzed data from 10,209 control and 9,625 case mothers. Among controls, the prevalence of exposure to DHFRI medications was 0.3% and to AEDs was 0.5%. Maternal use of AEDs was associated with increased risks for NTDs (OR: 3.4; 95% CI: 1.5, 7.5), oral clefts (OR: 2.3; 95% CI: 1.3, 4.0), urinary defects (OR: 1.6; 95% CI: 1.0, 2.7), and cardiac defects (OR: 1.6; 95% CI: 1.1, 2.3); similar or further increased risks were found among those with FA intake ≥400 mcg per day. DHFRI use was rare and relative risk estimates were imprecise and consistent with the null.

Conclusions

Similar to our previous analyses, we observed associations between AED use and these defects. For DHFRI exposure, we found no evidence for increased risk of these defects. Though statistical power to examine FA effect modification was low, we found no evidence of further protection among those with FA intake ≥400 mcg, with some associations somewhat stronger in this group.
Regulatory interventions improve the biosynthesis of limiting amino acids from methanol carbon to improve synthetic methylotrophy in Escherichia coli
Authors: Kyle Bennett Robert , Agee Alec , Har Jie R. G. , von Hagel Bryan , Antoniewicz Maciek R. , Papoutsakis Eleftherios T.
Published: September 2020

Synthetic methylotrophy aims to engineer methane and methanol utilization pathways in platform hosts like Escherichia coli for industrial bioprocessing of natural gas and biogas. While recent attempts to engineer synthetic methylotrophs have proved successful, autonomous methylotrophy, that is, the ability to utilize methane or methanol as sole carbon and energy substrates, has not yet been realized. Here, we address an important limitation of autonomous methylotrophy in E. coli: the inability of the organism to synthesize several amino acids when grown on methanol. We targeted global and local amino acid regulatory networks. Those include removal of amino acid allosteric feedback inhibition (argAH15Y, ilvAL447F, hisGE271K, leuAG462D, proBD107N, thrAS345F, trpES40F), knockouts of transcriptional repressors (ihfA, metJ); and overexpression of amino acid biosynthetic operons (hisGDCBHAFI, leuABCD, thrABC, trpEDCBA) and transcriptional regulators (crp, purR). Compared to the parent methylotrophic E. coli strain that was unable to synthesize these amino acids from methanol carbon, these strategies resulted in improved biosynthesis of limiting proteinogenic amino acids (histidine, leucine, lysine, methionine, phenylalanine, threonine, tyrosine) from methanol carbon. In several cases, improved amino acid biosynthesis from methanol carbon led to improvements in methylotrophic growth in methanol minimal medium supplemented with a small amount of yeast extract. This study addresses a key limitation currently preventing autonomous methylotrophy in E. coli and possibly other synthetic methylotrophs and provides insight as to how this limitation can be alleviated via global and local regulatory modifications.
Application of an LC–ESI–QTOF–MS method for evaluating clindamycin concentrations in plasma and prostate microdialysate of rats
Authors: Ritter Lisiani , Possa Eduarda , Bergoza Larissa , Agostini Fabiana , Silva Sidnei M. , Tasso Leandro
Published: September 2020

Clindamycin is used for infections caused by Gram‐positive and Gram‐negative anaerobic pathogens and Gram‐positive aerobes. Propionibacterium acnes is an important opportunistic microorganism of the human skin and is related to prostatitis. An LC–electrospray ionization–quadrupole time‐of‐flight–MS method was validated for determining clindamycin concentrations in plasma and prostate microdialysate. Clindamycin separation was carried out on a C18 column at 0.5 mL/min. The mobile phase employed gradient elution of formic acid and methanol. A mass spectrometer was operated in positive electrospray ionization mode to monitor ion 425.1784 and 253.1152 for clindamycin and cimetidine (internal standard), respectively. Linearity was obtained at 0.5–10.0 μg/mL (plasma) and 0.05–1.0 μg/mL (microdialysate) with coefficients of determination ≥0.999. The intra‐ and inter‐day precision (coefficient of variation ‐ CV%) values were ≤13.83% and 12.51% for plasma, respectively, and ≤10.90% and 9.35% for microdialysate, respectively. The accuracy was between 90.82% and 108.25% for plasma, and 96.97% and 106.98% for microdialysate. The present method was fully validated and applied to investigate clindamycin concentrations in both plasma and prostate by microdialysis in Wistar rats (80 mg/kg, intravenous). Because the penetration of antibiotics into the prostate may be restricted, this method allows us to investigate the prostate concentrations of clindamycin for the first time.
Clock‐drawing test: Normative data of three quantitative scoring methods for Chinese‐speaking adults in Shijiazhuang City and clinical utility in patients with acute ischemic stroke
Authors: Shao Kai , Dong Fang‐Ming , Guo Shang‐Zun , Wang Wei , Zhao Zhong‐Min , Yang Yi‐Ming , Wang Pan‐Pan , Wang Jian‐Hua
Published: September 2020

Objective

The clock‐drawing test (CDT) is a widely used screening tool for detecting cognitive decline. However, normative data for Chinese individuals are scarce. Our study aimed to provide standardized values for the three quantitative CDT scoring methods that were tailored for Chinese‐speaking adults in Shijiazhuang City and explore the discriminant validity of the CDT scores in patients with acute ischemic stroke.

Methods

We conducted the CDT among 418 healthy individuals aged between 35 and 84 years. The CDT was administered and scored by five raters using the method derived from the Montreal Cognitive Assessment (MoCA), Rouleau's, and Babins’ scoring systems. The influence of age, education, and sex on the performance in the CDT was analyzed. Furthermore, 336 patients with acute ischemic stroke were enrolled to explore the discriminant validity of CDT scores.

Results

In all three scoring systems, CDT scores were significantly correlated with age and years of education but not with sex. Normative data stratified for age and years of education were established. Interrater and intersystem reliability were high in our study. CDT total scores and subscores showed significant differences between stroke patients and healthy individuals.

Conclusions

Our study provides CDT normative data using three quantitative scoring methods for Chinese‐speaking adults in Shijiazhuang City. Age and education level were the key factors that affected the CDT scores. CDT total scores and subscores provided good discriminant validity for patients with acute ischemic stroke.
Multicultural investigation of the students' acceptance of using digital learning materials in laboratory classes
Authors: Sarsar Fırat , Kale Özge A. , Andiç‐Çakır Özge , Gueorguiev Tzvetelin , Evstatiev Boris , Georgieva Tsvetelina , Kadirova Seher , Mihailov Nikolay , Różewski Przemysław , Kieruzel Magdalena , Lipczyński Tomasz , Prys Marcin , van Leeuwen Manon
Published: September 2020

The digitalization of education is a continuously developing process, aimed at the use of information and communication technologies. However, engineering education utilizes several forms of learning, with laboratory experiments being one of them. The use of digital learning materials (DLM) in labs is still limited due to numerous existing factors. This study investigates students' acceptance of using DLM during laboratory exercises in three universities located in Turkey, Poland, and Bulgaria. A questionnaire was prepared, and a survey was conducted among 625 learners. They were divided into eight categories, based on their engineering area and country. The survey results demonstrate that there is a strong correlation between the students' opinion on DLM and the use of DLM by their lab instructors, which means that their acceptance could be increased if more DLM are integrated in lab courses. The analysis of the questionnaire results also showed that there is a significant difference in the students' opinion on DLM, depending on the engineering area. Students of Food, Chemistry, and Electrical engineering rated the use of DLM quite high (above 4.0 out of 5), followed by the Civil engineering students with average results between 3.5 and 4.0. Respondents involved in Textile, Bio, and Machine engineering were the most skeptical (<3.5). Furthermore, their opinions covered a wide range from “Strongly disagree” to “Strongly agree.”
Integrated activities in STEM environment: Methodology and implementation practice
Authors: Juškevičienė Anita , Dagienė Valentina , Dolgopolovas Vladimiras
Published: September 2020

Introduction

Science, Technology, Engineering, and Mathematics (STEM) and STEAM (with A for Arts) have evolved to symbolize the renewal of science education. STEAM education offers a number of benefits, such as improved problem analysis and solving skills, as well as the development of creative abilities. Many researchers reiterate the importance of STEAM‐related activities and programs, especially the integration of maker education. Despite much interest in STEAM, it is often challenging for many educators to incorporate integrated activities into their teaching practice. This paper deals with the value of STEAM integration in a methodological sense, with a focus on the maker's laboratory and physical computing, as well as the application of design thinking and computational thinking approaches.

Motivation and Objectives

The goal of this study is to develop a comprehensive conceptual framework for integrated STEM curricula focusing on the following research questions: (a) how to improve daily activities of STEM education by combining the activities of different laboratories and using a design thinking approach? and (b) how to combine FabLab activities and physical computing related to teaching different aspects of computational thinking in the context of STEM?

Research Methodology and Methods

As a research methodology, we implement a mixed methods strategy to combine theoretical study and empirical research based on a synthesized literature survey and the process of iterative model development based on an observational case study. We conduct a detailed case study of two applications of integrated activities based on FabLab and physical computing integration, and illustrate how design thinking can guide teachers to open up for interdisciplinary, creative, and project‐based opportunities.

Results and Findings

The paper provides a conceptual framework for STEM integration activities and step‐by‐step guidelines on how design thinking methods could could interact in practice. The implications of the results may be useful for educators seeking recommendations for the integration process, which enable educators to design hands‐on activities and incorporate integrated aspect of students' STEAM learning into teaching practice. In conclusions, the authors suggest that as interdisciplinary crossroads, design thinking provides a natural bridge between subjects, and fits especially to integrate activities of the maker's labs and physical computing, focusing on the integration of computational thinking and computational making approaches within STEM education environment. The absence of a statistical evaluation, which is positioned as a further research step, may be mentioned as a limitation of the study.
Fuzzy logic based performance analysis of educational mobile game for engineering students
Authors: Ozdemir Ali , Balbal Kadriye F.
Published: September 2020

The aim of this study is to examine the effect of an educational android mobile game on the attitude of engineering students. For this purpose, an educational mobile game is developed and a fuzzy logic based attitude determination system is modeled. The study is carried out with 30 students of mechatronic engineering. A mobile game which is called Select Box—Solve Question has been developed in the android studio environment. Besides this; to analyse the performance of the game on the success of education, a fuzzy logic‐based attitude determination system, which consists of four number of inputs and outputs, is modeled. These input and output values constitute the factors of the attitude scale. The Triangular Membership Function is used as the Fuzzification step of the Fuzzy Logic Technique. Four different defuzzification methods are used and the results of these methods are compared and analysed.
Timing of fluorodeoxyglucose positron emission tomography maximum standardized uptake value for diagnosis of local recurrence of non‐small cell lung cancer after stereotactic body radiation therapy
Authors: Tan Daren , Gill Suki , Loh Nelson
Published: September 2020

Introduction

After treatment with stereotactic body radiation therapy (SBRT), local recurrence of non‐small cell cancer (NSCLC) can be difficult to differentiate from radiation‐induced changes. Maximum standardized uptake value (SUVmax), measured with 18‐F‐Fluorodeoxyglucose positron emission tomography (FDG‐PET), can have false positives due to acute radiation inflammation. The primary study objective was to determine the utility of SUVmax > 5 to identify local recurrence later than 9 months after SBRT.

Method

A retrospective review was performed of FDG‐PET scans for suspicious CT findings after SBRT treatment of stage 1 NSCLC. SUVmax was measured including surrounding opacification. Outcome measures were local recurrence, progression free survival, and overall survival. Receiver operator curve analysis, sensitivity, specificity, and Kaplan‐Meier analysis were performed.

Results

Of 118 patients treated, 42 patients had eligible FDG‐PET scans. They received SBRT (48‐60Gy in 3‐8 fractions) for 49 NSCLC and had 101 follow‐up PET scans. The median time to first PET scan was 9.3 months, and the median follow‐up period was 22.4 months. Local recurrence was diagnosed in 12 patients, at a median of 16 months. Due to selection bias, the included patients had poorer outcomes than the entire cohort, with progression free survival (PFS) at 1, 2, and 3 years of 82.7%, 57.8%, and 45.8%; and overall survival of 97.9%, 79.9%, and 59.1%, respectively. Thirty FDG‐PET scans were performed within 9 months, of which 17% were false positives. A total of 71 FDG‐PET scans were performed beyond 9 months, and the median SUVmax was significantly higher for patients with local recurrence (7.48 vs. 2.14, P < .0001). SUVmax > 5 has a sensitivity of 91% (95% CI 62%‐99.8%) and 100% (89.1%‐100%).

Conclusion

For local recurrence of NSCLC, SUVmax > 5 on FDG‐PET scan has good sensitivity and specificity after 6 months, but is highest beyond 9 months after SBRT.
Investigating the impact of open label design on patient‐reported outcome results in prostate cancer randomized controlled trials
Authors: Mouillet Guillaume , Efficace Fabio , Thiery‐Vuillemin Antoine , Charton Emilie , Van Hemelrijck Mieke , Sparano Francesco , Anota Amélie
Published: September 2020

Background

While open‐label randomized controlled trials (RCT) are common in oncology, some concerns have been expressed with regard to Patient‐Reported Outcomes (PRO)‐based claims stemming from these studies. We aimed to investigate the impact of open‐label design in the context of prostate cancer (PCa) RCTs with PRO data.

Methods

Randomized controlled trials of PCa with a PRO endpoint published between 2004 and 2018 were considered. RCTs were systematically evaluated on the basis of previously defined criteria, including international PRO reporting quality standards and the Cochrane Collaboration's tool for assessing Risk of Bias. The rate of concordance was estimated and compared between traditional clinical outcomes (eg, survival or tumor response) and PRO in open and blinded RCTs.

Results

We identified 110 RCTs published between 2004 and 2018, of which 62% (n = 68) were open‐label. The general characteristics of PCa RCTs were not different according to their design (open‐label vs blinded). The proportion of PCa RCTs with high‐quality PRO reporting was not different between open‐label RCTs and blinded RCTs (41.2% vs 38.1%; P = .75). No statistically significant difference was found between PRO results and concordance with traditional clinical outcomes according to the study design.

Conclusion

Our findings suggest that there is no evidence of significant bias for PROs due to the absence of blinding in the context of PCa RCTs. Further analyses should be conducted in other cancer disease sites.
FASTSWARM: A data‐driven framework for real‐time flying insect swarm simulation
Authors: Xiang Wei , Yao Xinran , Wang He , Jin Xiaogang
Published: September 2020

Insect swarms are common phenomena in nature and therefore have been actively pursued in computer animation. Realistic insect swarm simulation is difficult due to two challenges: high‐fidelity behaviors and large scales, which make the simulation practice subject to laborious manual work and excessive trial‐and‐error processes. To address both challenges, we present a novel data‐driven framework, FASTSWARM, to model complex behaviors of flying insects based on real‐world data and simulate plausible animations of flying insect swarms. FASTSWARM has a linear time complexity and achieves real‐time performance for large swarms. The high‐fidelity behavior model of FASTSWARM explicitly takes into consideration the most common behaviors of flying insects, including the interactions among insects such as repulsion and attraction, self‐propelled behaviors such as target following and obstacle avoidance, and other characteristics such as random movements. To achieve scalability, an energy minimization problem is formed with different behaviors modeled as energy terms, where the minimizer is the desired behavior. The minimizer is computed from the real‐world data, which ensures the plausibility of the simulation results. Extensive simulation results and evaluations show that FASTSWARM is versatile in simulating various swarm behaviors, high fidelity measured by various metrics, easily controllable in inducing user controls and highly scalable.
Developments in Mannose‐Based Treatments for Uropathogenic Escherichia coli‐Induced Urinary Tract Infections
Authors: Hatton Natasha E. , Baumann Christoph G. , Fascione Martin A.
Published: September 2020

During their lifetime almost half of women will experience a symptomatic urinary tract infection (UTI) with a further half experiencing a relapse within six months. Currently UTIs are treated with antibiotics, but increasing antibiotic resistance rates highlight the need for new treatments. Uropathogenic Escherichia coli (UPEC) is responsible for the majority of symptomatic UTI cases and thus has become a key pathological target. Adhesion of type one pilus subunit FimH at the surface of UPEC strains to mannose‐saturated oligosaccharides located on the urothelium is critical to pathogenesis. Since the identification of FimH as a therapeutic target in the late 1980s, a substantial body of research has been generated focusing on the development of FimH‐targeting mannose‐based anti‐adhesion therapies. In this review we will discuss the design of different classes of these mannose‐based compounds and their utility and potential as UPEC therapeutics.
Enhancing Biosynthesis and Manipulating Flux in Whole Cells with Abiotic Catalysis
Authors: Stewart Kelsey N. , Domaille Dylan W.
Published: September 2020

Metabolic engineering uses genetic strategies to drive flux through desired pathways. Recent work with electrochemical, photochemical, and chemocatalytic setups has revealed that these systems can also expand metabolic pathways and manipulate flux in whole cells. Electrochemical systems add or remove electrons from metabolic pathways to direct flux to more‐ or less‐reduced products. Photochemical systems act as synthetic light‐harvesting complexes and yield artificial photosynthetic organisms. Biocompatible chemocatalysis increases product scope, streamlines syntheses, and yields single‐flask processes to deliver products that would be challenging to synthesize through biosynthetic means alone. Here, we exclusively highlight systems that combine abiotic systems with living whole cells, taking particular note of strategies that enable the merger of these typically disparate systems.
Activity‐Based Protein Profiling (ABPP) of Oxidoreductases
Authors: Fuerst Rita , Breinbauer Rolf
Published: September 2020

Over the last two decades, activity‐based protein profiling (ABPP) has been established as a tremendously useful proteomic tool for measuring the activity of proteins in their cellular context, annotating the function of uncharacterized proteins, and investigating the target profile of small‐molecule inhibitors. Unlike hydrolases and other enzyme classes, which exhibit a characteristic nucleophilic residue, oxidoreductases have received much less attention in ABPP. In this minireview, the state of the art of ABPP of oxidoreductases is described and the scope and limitations of the existing approaches are discussed. It is noted that several ABPP probes have been described for various oxidases, but none so far for a reductase, which gives rise to opportunities for future research.
TP53 and PTEN as driver mutations in Zenker's carcinoma—a clinical presentation
Authors: Noel Zsanett , Hoeller Sylvia , Bihl Michel , Muller Laurent
Published: September 2020

Zenker carcinoma is still being treated empirically because of the lack of evidence‐ based guidelines. We report for the first time about the genetic examination of this rare entity. The revealed mutations show genetic similarities with HPV(‐)HNSCC which suggests that well‐known therapeutic strategies may be applicable for this disease
A case of mild‐to‐intermediate left‐main lesion with high‐risk plaque features: “Blindness of physiology” for PCI guidance?
Authors: Al‐Nooryani Arif , Aboushokka Wael , Mehmedbegovic Zlatko , Beleslin Branko
Published: September 2020

In patients presenting with acute coronary syndrome without ST elevation, both FFR and OCT imaging may be necessary to adequately interrogate patients with intermediate and ambiguous left‐main coronary stenosis.
Azobenzene‐Based Low‐Potential Anolyte for Nonaqueous Organic Redox Flow Batteries
Authors: Wang Xiao , Chai Jingchao , Lashgari Amir , Jiang Jianbing Jimmy
Published: September 2020

Redox flow batteries (RFBs) using organic materials in organic solvents are particularly promising because of the diversity of organic materials and the wide redox‐innocent window of organic solvents, yet the further development of this type of RFB has been hindered by the lack of suitable anolyte materials with high potentials, solubility, and stability. Herein, we examine the physical and electrochemical properties of azobenzene (AzoPh) compounds and investigate their degradation mechanism in nonaqueous organic RFB. The azobenzene displayed two‐electron activity at −1.69 and −2.20 V vs. Ag/Ag+. Paired with a well‐established PEGylated phenothiazine (PEG3‐PTZ ) catholyte, the battery presents a high theoretical cell voltage of 2.08 V. The azobenzene‐based RFB displays a capacity retention of 93.3 % over 50 cycles with an average fade rate of 0.13 % per cycle. The capacity decay mechanism was probed by proton nuclear magnetic resonance spectroscopy, cyclic voltammetry, and high‐resolution mass spectrometry, and revealed proton‐assisted degradation mechanisms.
Synthesis and Optimization of Zeolitic Imidazolate Frameworks for the Oxygen Evolution Reaction
Authors: Li Juntao , Gadipelli Srinivas
Published: September 2020

Metal–organic frameworks/zeolitic imidazolate frameworks (MOFs/ZIFs) and their post‐synthesis modified nanostructures, such as oxides, hydroxides, and carbons have generated significant interest for electrocatalytic reactions. In this work, a high and durable oxygen evolution reaction (OER) performance directly from bimetallic Zn100−xCox‐ZIF samples is reported, without carrying out high‐temperature calcination and/or carbonization. ZIFs can be reproducibly and readily synthesized in large scale at ambient conditions. The bimetallic ZIFs show a systematic and gradually improved OER activity with increasing cobalt concentration. A further increase in OER activity is evidenced in ZIF‐67 polyhedrons with controlled particle size of <200 nm among samples of different sizes between 50 nm and 2 μm. Building on this, a significantly enhanced, >50 %, OER activity is obtained with ZIF‐67/carbon black, which shows a low overpotential of approximately 320 mV in 1.0 m KOH electrolyte. Such activity is comparable to or better than numerous MOF/ZIF‐derived electrocatalysts. The optimized ZIF‐67 sample also exhibits increased activity and durability over 24 h, which is attributed to an in situ developed active cobalt oxide/oxyhydroxide related nanophase.
Allosteric Control of Naphthalene Diimide Encapsulation and Electron Transfer in Porphyrin Containers: Photophysical Studies and Molecular Dynamics Simulation
Authors: Zanetti‐Polzi Laura , Djemili Ryan , Durot Stéphanie , Heitz Valérie , Daidone Isabella , Ventura Barbara
Published: September 2020

The complexation processes of N,N’‐dibutyl‐1,4,5,8‐naphthalene diimide (NDI) into two types of π‐electron‐rich molecular containers consisting of two Zn(II)‐porphyrins connected by four flexible linkers of two different lengths, were characterized by means of absorption and emission spectroscopies and molecular dynamics simulation. Notably, the addition of NDI leads to a strong quenching of the fluorescence of both cages only when they are in an open conformation suitable for guest encapsulation, a situation triggered by silver(I) ions binding to the lateral triazoles. Molecular dynamics simulations confirm the fast binding of NDI, likely assisted by NDI‐silver(I) interactions. Upon NDI complexation, the two porphyrin macrocycles get closer, with an optimized face to face orientation, suggesting an induced‐fit mechanism through π–π interactions with the NDI aromatic cycle. Ultrafast transient absorption experiments allowed to identify the process of quenching of the Zn‐porphyrin fluorescence as an efficient photoinduced electron transfer reaction between the cage porphyrin and the included NDI guest. The process occurs on fast and ultrafast time scales in the two complexes (1.5 ps and ≤300 fs) leading to a short‐lived charge separated state (charge recombination lifetimes in the order of 30–40 ps). The combined computational and experimental approach used here is able to furnish a reliable model of the NDI‐cage complexation mechanism and of the corresponding electron transfer reaction, attesting the allosteric control of both processes by the silver(I) ions.
Deposition of the Spin Crossover FeII–Pyrazolylborate Complex on Au(111) Surface at the Molecular Level
Authors: Montenegro‐Pohlhammer Nicolás , Sánchez‐de‐Armas Rocío , Calzado Carmen J.
Published: September 2020

The interaction at the molecular level of the spin‐crossover (SCO) FeII((3,5‐(CH3)2Pz)3BH)2 complex with the Au(111) surface is analyzed by means of rPBE periodic calculations. Our results show that the adsorption on the metallic surface enhances the transition energy, increasing the relative stability of the low spin (LS) state. The interaction indeed is spin‐dependent, stronger for the low spin than the high spin (HS) state. The different strength of the Fe ligand field at low and high temperature manifests on the nature, spatial extension and relative energy of the states close to the Fermi level, with a larger metal–ligand hybridization in the LS state. This feature is of relevance for the differential adsorption of the LS and HS molecules, the spin‐dependent conductance, and for the differences found in the corresponding STM images, correctly reproduced from the density of states provided by the rPBE calculations. It is expected that this spin dependence will be a general feature of the SCO molecule–substrate interaction, since it is rooted in the different ligand field of Fe site at low and high temperatures, a common hallmark of the FeII SCO complexes. Finally, the states involved in the LIESST phenomenon has been identified through NEVPT2 calculations on a model reaction path. A tentative pathway for the photoinduced LS→HS transition is proposed, that does not involve the intermediate triplet states, and nicely reproduces both the blue laser wavelength required for the activation, and the wavelength of the reverse HS → LS transition.
Doubly Protective MOF‐Photo‐Fabrics: Facile Template‐Free Synthesis of PCN‐222‐Textiles Enables Rapid Hydrolysis, Photo‐Hydrolysis and Selective Oxidation of Multiple Chemical Warfare Agents and Simulants
Authors: Barton Heather F. , Jamir Jovenal D. , Davis Alexandra K. , Peterson Gregory W. , Parsons Gregory N.
Published: September 2020

New materials and chemical knowledge for improved personal protection are among the most pressing needs in the international community. Reported attacks using chemical warfare agents (CWAs,) including organophosphate soman (GD) and thioether mustard gas (HD) are driving research in field‐deployable catalytic composites for rapid toxin degradation. In this work, we report simple template‐free low temperature synthesis that enables for the first time, a deployable‐structured catalytic metal‐organic framework/polymer textile composite “MOF‐fabric” showing rapid hydrolysis and oxidation of multiple active chemical warfare agents, GD and HD, respectively, and their simulants. Our method yields new zirconium–porphyrin based nano‐crystalline PCN‐222 MOF‐fabrics with adjustable MOF loading and robust mechanical adhesion on low‐cost nonwoven polypropylene fibers. Importantly, we describe quantitative kinetic analysis confirming that our MOF‐fabrics are as effective as or better than analogous MOF powders for agent degradation, especially for oxidation. Faster oxidation using the MOF‐fabrics is ascribed to the composite geometry, where active MOF catalysts are uniformly displayed on the MOF‐textile enabling better reactant transport and reactive oxidant generation. Furthermore, we note the discovery of visible photo‐activation of GD hydrolysis by a MOF‐fabric, which is ascribed to oxidation at the active metal node site, significantly increasing the rate over that observed without illumination. These results provide important new insights into the design of future materials and chemical systems to protect military, first‐responders, and civilians upon exposure to complex chemical toxins.
Strategies of Removing Residual Lithium Compounds on the Surface of Ni‐Rich Cathode Materials†
Authors: Su Yuefeng , Li Linwei , Chen Gang , Chen Lai , Li Ning , Lu Yun , Bao Liying , Chen Shi , Wu Feng
Published: September 2020

Ni‐rich cathode materials have become one of the most promising cathode materials for advanced high‐energy Li‐ion batteries (LIBs) owing to their high specific capacity. However, Ni‐rich cathode materials are sensitive to the trace H2O and CO2 in the air, and tend to react with them to generate LiOH and Li2CO3 at the particle surface region (named residual lithium compounds, labeled as RLCs). The RLCs will deteriorate the comprehensive performances of Ni‐rich cathode materials and make trouble in the subsequent manufacturing process of electrode, including causing low initial coulombic efficiency and poor storage property, bringing about potential safety hazards, and gelatinizing the electrode slurry. Therefore, it is of considerable significance to remove the RLCs. Researchers have done a lot of work on the corresponding field, such as exploring the formation mechanism and elimination methods. This paper investigates the origin of the surface residual lithium compounds on Ni‐rich cathode materials, analyzes their adverse effects on the performance and the subsequent electrode production process, and summarizes various kinds of feasible methods for removing the RLCs. Finally, we propose a new research direction of eliminating the lithium residuals after comparing and summing up the above. We hope this work can provide a reference for alleviating the adverse effects of residual lithium compounds for Ni‐rich cathode materials’ industrial production.
Development of Novel 4‐Arylpyridin‐2‐one and 6‐Arylpyrimidin‐4‐one Positive Allosteric Modulators of the M1 Muscarinic Acetylcholine Receptor
Authors: Jörg Manuela , Khajehali Elham , van der Westhuizen Emma T. , C. Choy K. H. , Shackleford David M. , Tobin Andrew B. , Sexton Patrick M. , Valant Celine , Capuano Ben , Christopoulos Arthur , Scammells Peter J.
Published: September 2020

This study investigated the structure‐activity relationships of 4‐phenylpyridin‐2‐one and 6‐phenylpyrimidin‐4‐one M1 muscarinic acetylcholine receptor (M1 mAChRs) positive allosteric modulators (PAMs). The presented series focuses on modifications to the core and top motif of the reported leads, MIPS1650 (1) and MIPS1780 (2). Profiling of our novel analogues showed that these modifications result in more nuanced effects on the allosteric properties compared to our previous compounds with alterations to the biaryl pendant. Further pharmacological characterisation of the selected compounds in radioligand binding, IP1 accumulation and β‐arrestin 2 recruitment assays demonstrated that, despite primarily acting as affinity modulators, the PAMs displayed different pharmacological properties across the two cellular assays. The novel PAM 7 f is a potential lead candidate for further development of peripherally restricted M1 PAMs, due to its lower blood–brain‐barrier (BBB) permeability and improved exposure in the periphery compared to lead 2.
Spectator‐filter‐spreader‐stifler information propagation model with wake‐up mechanism in social networks
Authors: Liu Shuqi , Sun Chengai , Qiu Liqing , Wei Moji
Published: September 2020

Nowadays, social network platforms play a significant role in daily life, allowing people to hear what is going on around the world without leaving home. The research on the internal transformation of information propagation is critical, which can help restrain the propagation of fake information or rumors and promote the widespread dissemination of effective information. To better understand the transition of states in information propagation, this article considers a new filter state that does not transmit information temporarily and establishes a spectator‐filter‐spreader‐stifler (SFIR) model. Mainly, to explore the dynamics of information propagation, the article introduces two different wake‐up mechanisms including the spontaneous awakening of the filter and the infection of the leader spreaders to the passive stifler, which relies on the proportion of current spreaders as well as the doubt degree on information. Afterward, based on the average field equations built, the nonpropagation equilibrium point E0 and propagation equilibrium point E1 are obtained by theoretical analysis. Moreover, the simulation results reveal that spontaneous wake‐up mechanism accelerates the information propagation while leader spreaders infection increases the scope of information propagation, which can provide theoretical support for controlling information propagation more effectively.
Suicide‐related interpersonal needs of young Iranian people: A preliminary validation of thwarted belongingness and perceived burdensomeness constructs
Authors: Amini‐Tehrani Mohammadali , Sadeghi Raheleh , Nasiri Mohammad , Jalali Tina , Zamanian Hadi
Published: September 2020

The aim of the current study was to validate the Interpersonal Needs Questionnaire (INQ‐15) and to test its reliability in Persian‐speaking Iranian undergraduate students. In this cross‐sectional study, 485 undergraduate students (age: 20.66 ± 1.42, 60% female) were assessed on the two subscales of perceived burdensomeness (PB) and thwarted belongingness (TB) and the Suicide Behavior Questionnaire‐Revised (SBQ‐R). Exploratory structural equation modelling (ESEM) confirmed the construct validity of INQ‐14, excluding INQ#9. In addition, INQ#8, articulated in an equivalent Persian phrasing, loaded well on TB. The measurement model tested by confirmatory factor analysis (CFA) suggested INQ#11 to be eliminated, resulting in INQ‐13‐P to consist of PB and TB‐7. The internal consistency and convergent/discriminant validity were established. The concurrent validity of PB was solidly established in terms of past year suicidal ideation (PY‐SI) above and beyond anxiety, depression, prior suicidality, and TB‐7. The effect of PB on PY‐SI was stronger, where prior suicidality had already occurred or the perceived likelihood of future suicide (PLFS) was high. Moreover, TB‐7 could only indicate PY‐SI, where prior suicidality had already occurred or PLFS was high, albeit when PB was omitted. The interaction term was significant; however, beyond anxiety and depression, the effect of TB‐7 on PY‐SI was significant where PB was very high (n = 40, 8.25%). Therefore, future studies can utilize INQ‐13‐P as a valid and reliable instrument in Persian‐speaking populations. However, further studies should examine the construct validity of TB and its relationship with suicide ideation in different populations.
Emerging Potassium‐ion Hybrid Capacitors
Authors: Liu Meiqi , Chang Limin , Le Zaiyuan , Jiang Jiangmin , Li Jiahui , Wang Hairui , Zhao Cuimei , Xu Tianhao , Nie Ping , Wang Limin
Published: September 2020

As a new type of capacitor–battery hybrid energy storage device, metal‐ion capacitors have attracted widespread attention because of their high‐power density while ensuring energy density and long lifespan. Potassium‐ion capacitors (KICs) featuring the merits of abundant potassium resources, lower standard electrode potential, and low cost have been considered as potential alternatives to lithium‐/sodium‐ion capacitors. However, KICs still face issues including unsatisfactory reaction kinetics, low energy density, and poor lifetime owing to the large radius of the potassium ion. In this Review, the importance of emerging potassium‐ion capacitor is addressed. The Review offers a brief discussion of the fundamental working principle of KICs, along with an overview of recent advances and achievements of a variety of electrode materials for dual carbon and non‐dual carbon KICs. Furthermore, electrolyte chemistry, binders as well as electrode/electrolyte interface, are summarized. Finally, existing challenges and perspectives on further development of KICs are also presented.
Highly Reversible Na‐Intercalation into Graphite Recovered from Spent Li–Ion Batteries for High‐Energy Na‐Ion Capacitor
Authors: Divya Madhusoodhanan Lathika , Natarajan Subramanian , Lee Yun‐Sung , Aravindan Vanchiappan
Published: September 2020

High‐performance Na‐ion capacitor (NIC) was constructed with graphite recovered from spent Li‐ion batteries (LIBs) as battery‐type negative electrode and high‐surface‐area activated carbon as a supercapacitor component. Unlike Li‐insertion into graphite, Na‐insertion into graphite is extremely limited; hence, a “solvent‐co‐intercalation” mechanism was proposed for high reversibility using ether family solvents. First, the Na‐insertion properties were assessed in the half‐cell assembly with 0.5 m NaPF6 in tetraethylene glycol dimethyl ether as an electrolyte solution and compared with the commercial graphite. The NIC comprised pre‐sodiated graphite as a negative electrode and commercial activated carbon as a cathode. This fascinating NIC configuration displayed the maximum energy density of 59.93 Wh kg−1 with exceptional cyclability of 5000 cycles at ambient temperature with approximately 98 % retention. Interestingly, the electrode aging process in the presence of electrolyte resulted in approximately 19 % higher energy density than the routine electrode heat treatment. Further, the electrochemical activity of the NIC at various temperatures was studied, and it was found that the graphite recovered from spent LIBs could be effectively reused towards the construction of high‐performance charge storage devices with exceptional performance.