bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of Carbon Porosity on Sulfur Conversion in Li−S Battery Cathodes in a Sparingly Polysulfide Solvating Electrolyte
Authors: Kensy Christian , Schwotzer Friedrich , Dörfler Susanne , Althues Holger , Kaskel Stefan
Published: February 2021

Advancing the development of lithium‐sulfur (Li−S) technology is advantageous for next generation secondary batteries to improve gravimetric and volumetric energy of established energy storage devices. In this regard, a sparingly PS solvating electrolyte based on sulfolane and hydrofluoroether is known as a promising concept to enhance the volumetric energy density by increasing the cycling stability. So far, little is known about the impact of the carbon porosity on the electrochemical sulfur utilization. Herein, carbon materials with varying pore diameter and architecture (micropores, mesopores and hierarchical pores) are studied as scaffold for Li−S cathodes using TMS/TTE electrolyte to obtain more insights into the relationship between the carbon scaffold porosity and the modified conversion mechanism of sparingly solvating electrolytes. The electrochemical evaluation under lean conditions (5 μl mgS−1) revealed stable cycling performance for all Li−S cathodes. Using microporous electrodes, a reversible quasi‐solid‐state conversion is detected by an additional third discharge plateau being confirmed by cyclovoltammetry. GITT experiments give evidence that the carbon porosity impacts the reaction kinetics of the polysulfide conversion by using TMS/TTE electrolyte. Based on these findings, new mechanistic insights into the operation of Li−S batteries are provided by using sparingly solvating electrolytes.
Achieving a low human dose for targeted covalent drugs: Pharmacokinetic and pharmacodynamic considerations on target characteristics and drug attributes
Authors: Yang Zheng
Published: February 2021

Covalent modifications of off‐target biomolecules remain to be a concern for targeted covalent drugs. To guide the design of targeted covalent drugs in achieving a low human daily dose, a pharmacokinetic/pharmacodynamic (PK/PD) model was established to quantitatively evaluate target characteristics and drug properties that affect the human dose. Target characteristics, such as expression levels, turnover, and degree of inhibition relevant to efficacy, were evaluated systematically using the model. The drug properties including inactivation potency and drug clearance were also examined. Model simulations revealed that the interplay of target characteristics and drug properties governed the human dose. Particularly, the extent and the duration of target inactivation meaningful to efficacy, as well as the target resynthesis rate measured as the target turnover half‐life, needed to be determined. The target information then served as a basis to inform desired drug inactivation potency and PK properties. The model‐based approach provided a theoretical framework in achieving a low human dose of targeted covalent drugs, and the resultant strategy was successfully applied in the early stage of a Bruton's tyrosine kinase covalent inhibitor project that discovered low‐dose branebrutinib. The PK/PD considerations described are also applicable to the drug design for protein degraders that share the same endpoint as targeted covalent drugs in reducing target levels.
Acardiac twin pregnancies part V: Why does an acardiac twin with renal tissue produce polyhydramnios?
Authors: van Gemert Martin J. C. , Nikkels Peter G. J. , Ross Michael G. , van den Wijngaard Jeroen P. H. M.
Published: February 2021

Background

Acardiac twinning is a complication of monochorionic twin pregnancies. From literature reports, 30 of 41 relatively large acardiac twins with renal tissue produced polyhydramnios within their amniotic compartment. We aim to investigate the underlying mechanisms that cause excess amniotic fluid using an established model of fetal fluid dynamics.

Methods

We assumed that acardiac onset is before 13 weeks, acardiacs with renal tissue have normal kidney function and produce urine flow from 11 weeks on, and acardiac urine production requires a pressure of half the pump twin's mean arterial pressure. We apply a resistance network with the pump twin's arterio‐venous pressure as source, pump umbilical arteries, placenta, placental arterio‐arterial (AA) anastomoses and acardiac resistances. Acardiac amniotic fluid dynamics excluded acardiac lung fluid secretion, swallowing and the relatively small intramembranous flow.

Results

In small acardiacs with sufficient urine production, polyhydramnios will occur due to the lack of amniotic fluid resorption. Urine production is dependent upon having sufficient mean arterial pressure, which requires nearly a two‐fold larger resistance within the acardiac as compared to the placental AA resistance. Subphysiologic arterial pressure may result in renal dysgenesis.

Conclusion

Our findings suggest the potential for prediction of which clinical acardiac cases may or may not develop polyhydramnios based upon noninvasive assessments of renal tissue, blood flow and urine production. This information would be of great value in determining early obstetric interventions as opposed to conservative management. These findings may also contribute to an improved knowledge of the fascinating pathophysiology that surrounds acardiac twinning.
Assessment on the binding characteristics of residual marbofloxacin in animal‐derived food to bovine/human serum albumin by spectroscopy and molecular modelling
Authors: Li Xu , Yuan Yue , Zhao Rui , Shao Di , Bi Shuyun
Published: February 2021

To assess the toxicity of residual marbofloxacin from animal‐derived food, the interaction characteristics of marbofloxacin to bovine/human serum albumins (BSA/HSA) were explored using spectroscopic methods combined with molecular modelling. According to fluorescence spectra and time‐resolved fluorescence spectra measurements, quenching of BSA/HSA fluorescence induced by marbofloxacin was characterized as static quenching. A 1:1 ground‐state complex of marbofloxacin to BSA/HSA was formed with binding constant (Ka) 1.66 × 104/9.74 × 103 M−1 at 291 K. The location of marbofloxacin binding at site I within BSA/HSA was clarified by site marker competitive experiments. Molecular modelling demonstrated that the binding region for marbofloxacin to BSA and HSA were at site I with the lowest binding free energies of −22.86 and −21.60 kJ mol−1, respectively. Hydrogen bonds and van der Waals forces were dominantly involved in the spontaneous binding. Nonradiation energy transferred from BSA and HSA to marbofloxacin, due to the close distance (r0) between marbofloxacin and Trp residues of BSA (4.28 nm) and HSA (3.34 nm). As explained by circular dichroism (CD) spectra, an increased BSA/HSA α‐helix structure was observed after binding to marbofloxacin. Ultraviolet–visible (UV–vis) and Fourier transform infrared (FT‐IR) spectra suggested that conformation of the two proteins was altered by marbofloxacin.
Modeling coordinated enzymatic control of saccharification and fermentation by Clostridium thermocellum during consolidated bioprocessing of cellulose
Authors: Ahamed Firnaaz , Song Hyun‐Seob , Ho Yong Kuen
Published: February 2021

Consolidated bioprocessing (CBP) of cellulose is a cost‐effective route to produce valuable biochemicals by integrating saccharification, fermentation and cellulase synthesis in a single step. However, the lack of understanding of governing factors of interdependent saccharification and fermentation in CBP eludes reliable process optimization. Here, we propose a new framework that synergistically couples population balances (to simulate cellulose depolymerization) and cybernetic models (to model enzymatic regulation of fermentation) to enable improved understanding of CBP. The resulting framework, named the unified cybernetic‐population balance model (UC‐PBM), enables simulation of CBP driven by coordinated control of enzyme synthesis through closed‐loop interactions. UC‐PBM considers two key aspects in controlling CBP: (1) heterogeneity in cellulose properties and (2) cellular regulation of competing cell growth and cellulase secretion. In a case study on Clostridium thermocellum, UC‐PBM not only provides a decent fit with various exometabolomic data, but also reveals that: (i) growth‐decoupled cellulase‐secreting pathways are only activated during famine conditions to promote the production of growth substrates, and (ii) starting cellulose concentration has a strong influence on the overall flux distribution. Equipped with mechanisms of cellulose degradation and fermentative regulations, UC‐PBM is practical to explore phenotypic functions for primary evaluation of microorganisms’ potential for metabolic engineering and optimal design of bioprocess.
Synergising biomass growth kinetics and transport mechanisms to simulate light/dark cycle effects on photo‐production systems
Authors: Anye Cho Bovinille , de Carvalho Servia Miguel Ángel , del Río Chanona Ehecatl Antonio , Smith Robin , Zhang Dongda
Published: February 2021

Light attenuation is a primary challenge limiting the upscaling of photobioreactors for sustainable bio‐production. One key to this challenge, is to model and optimise the light/dark cycles so that cells within the dark region can be frequently transferred to the light region for photosynthesis. Therefore, this study proposes the first mechanistic model to integrate the light/dark cycle effects into biomass growth kinetics. This model was initially constructed through theoretical derivation based on the intracellular reaction kinetics, and was subsequently modified by embedding a new parameter, effective light coefficient, to account for the effects of culture mixing. To generate in silico process data, a new multiscale reactive transport modelling strategy was developed to couple fluid dynamics with biomass growth kinetics and light transmission. By comparing against previous experimental and computational studies, the multiscale model shows to be of high accuracy. Based on its simulation result, an original correlation was proposed to link effective light coefficient with photobioreactor gas inflow rate; this has not been done before. The impact of this study is that by using the proposed mechanistic model and correlation, we can easily control and optimise photobioreactor gas inflow rates to alleviate light attenuation and maintain a high biomass growth rate.
High‐rate ethanol production at low pH using the anaerobic granular sludge process
Authors: Tamis Jelmer , Joosse Bart , de Leeuw Kasper , Kleerebezem Robbert
Published: February 2021

In this study, we investigated the operational performance and product spectrum of glucose‐fermenting anaerobic granular sludge reactor at pH 4. A selective environment for the growth of granules was implemented by the introduction of a 2 min settling phase, a hydraulic retention time of 6 h and a solid retention time of 12 ± 3 days. The fermentation products were ethanol, lactate, and volatile fatty acids (VFA) with yields of 0.55 ± 0.03, 0.15 ± 0.02, and 0.20 ± 0.04 gram chemical oxygen demand (gCOD)/gCOD glucose, respectively. The obtained product spectrum was remarkably different from the VFA‐dominated product spectrum reported in a previous study when the same system was operated at higher pH (4.5–5.5). The shift in product spectrum coincided with a shift in the microbial community structure with the dominance of eukaryotic Candida tropicalis, Pichia jaroonii, and prokaryotic Lactobacillus species instead of the Clostridia species obtained at higher pH‐values. The control of the microbiomes and the associated product spectra provides bioprocess engineers with the option to tailor a suitable precursor compound mixture for subsequent chain elongation fermentation or PHA biopolymer production.
Stereoselective Carbocyclization of Vinyloxiranes Catalyzed by Lewis Acids: Construction of the Musellarin Tricyclic Core
Authors: Yang Sehui , Park Euijin , Kim Jimin
Published: February 2021

Stereoselective carbocyclizations of vinyloxiranes were efficiently catalyzed by Lewis acids to provide cyclic homoallyl alcohols as single isomers. The choice of Lewis acid, B(C6F5)3 was crucial for the stereoselective transformation in the case of cis vinyloxiranes, whereas BF3∙OEt2 was proven to be an effective catalyst for trans substrates. The method was well implemented in the synthesis of seven‐membered rings and six‐membered rings with functional group tolerance. Utility of the resulting trans‐ and cis homoallyl alcohols was demonstrated to concisely build the tricyclic core of musellarin A and E.
An Efficient Synthesis of (1‐Methyl)‐2‐phenyl‐4‐quinolones from (N‐Methyl)isatoic Anhydride
Authors: In Lee Jae
Published: February 2021

The acyl substitution of (N‐methyl)isatoic anhydride with N,O‐dimethylhydroxylamine hydrochloride in CH3CN gave N‐methoxy‐N‐methyl 2‐(N‐methyl)aminobenzamide, which was treated with ethynyllithium reagents to afford 1‐[2‐(N‐methyl)amino]‐3‐phenyl‐2‐propyn‐1‐ones. The 6‐endo cyclization of 1‐[2‐(N‐methyl)amino]‐3‐phenyl‐2‐propyn‐1‐ones using NaOCH3 in CH3OH at 65 °C gave various (1‐methyl)‐2‐phenyl‐4‐quinolone derivatives in high yields.
Pharmacokinetics profiles of polyphyllin II and polyphyllin VII in rats by liquid chromatography with tandem mass spectrometry
Authors: Wang Genbei , Hao Ruijia , Luo Chen , Wang Yu , Man Shuli , Gao Wenyuan
Published: February 2021

Polyphyllin II (PII) and polyphyllin VII (PVII) are the main active ingredients in Paris Polyphylla with an excellent antitumor effect in vitro and in vivo. In this study, a rapid and precise LC–MS/MS method was developed and validated for the separation and simultaneous determination of PII and PVII in rat plasma, tissues, feces and urine using ginsenoside Rg3 as the internal standard. Positive linearity ranged from 1 to 1,000 ng/ml in samples. At the same time, intra‐ and inter‐day precisions were in range of 1.8–12.0%. The accuracy ranged from 95.9 to 100.8%. Mean extraction recoveries of PII and PVII ranged from 86.6 to 96.4%. The analytical method has been successfully applied to the pharmacokinetic studies of PII and PVII in rats after their i.v. administration. After entering systemic circulation, PII and PVII were rapidly distributed in organs, mainly including liver, lung and spleen. Their elimination rate was slow. All of these data provided a theoretical basis for the application of PII and PVII in the treatment of liver‐ and lung‐related diseases.
Open‐label study with the monoamine stabilizer (‐)‐OSU6162 in myalgic encephalomyelitis/chronic fatigue syndrome
Authors: Haghighi Sara , Forsmark Sara , Zachrisson Olof , Carlsson Arvid , Nilsson Marie K. L. , Carlsson Maria L. , Schuit Robert C. , Gottfries Carl‐Gerhard
Published: February 2021

Objectives

The purpose of the present study was to investigate the safety and tolerability of the monoaminergic stabilizer (‐)‐OSU6162 in patients with myalgic encephalomyelitis/chronic fatigue syndrome (ME/CFS). In addition, a potential therapeutic effect of (‐)‐OSU6162 in ME/CFS was evaluated by means of observer‐rated scales and self‐assessment rating scales.

Materials and Methods

In the current study using an open‐label single‐arm design ME/CFS patient received treatment with (‐)‐OSU6162 during 12 weeks. The patients received the following doses of (‐)‐OSU6162: 15 mg b.i.d. during the first 4‐week period, up to 30 mg b.i.d. during the second 4‐week period and up to 45 mg b.i.d. during the third 4‐week period, with follow‐up visits after 16 and 20 weeks.

Results

Out of 33 included patients, 28 completed the 12 weeks treatment period. (‐)‐OSU6162 was well tolerated; only one patient discontinued due to an adverse event. Vital signs and physical examinations showed no abnormal changes. Blood analyses showed an increase in serum prolactin. Therapeutically, improvements were seen on the Clinical Global Impression of Change scale, the FibroFatigue scale, the Mental Fatigue Scale, the Fatigue Severity Scale, Beck Depression Inventory, and the Short Form 36 Health Survey Questionnaire.

Conclusions

(‐)‐OSU6162 is well tolerated in ME/CFS patients and shows promise as a novel treatment to mitigate fatigue and improve mood and health‐related quality of life in ME/CFS. Obviously, the present results need to be confirmed in future placebo‐controlled double‐blind trials.
Representative account or greenwashing? Voluntary sustainability reports in Australia's mining/metals and financial services industries
Authors: Zharfpeykan Ramona
Published: February 2021

Why are more and more companies voluntarily issuing costly, potentially exposing standalone sustainability reports on environmentally and socially problematic issues? Using legitimacy theory, this study analyses ways companies seek to strategically enhance legitimacy by leaning towards either ‘representative’ reporting of both favourable and unfavourable information especially in an industry's highest impact domains, or ‘greenwashing’ (including whitewashing non‐environmental issues), which downplays unfavourables and high‐impact domains and highlights favourable but less relevant points. Content analysis compared Global Reporting Initiatives (GRI) reports from 2011 to 2019 by Australian financial services companies (107 reports) and mining and metals companies (122). Specifically, to critique reporting quality in fine grain, it disaggregated results into levels (from omission to full quantitative treatment) of disclosure of good/bad/neutral news indicators and violation‐related/non‐violation‐related ones and identified highest impact domains. Neither industry's reporting was very representative. Relatively though, mining and metals leant towards representation: fuller disclosure on environmental aspects (its highest impact domain), including unfavourables: bad and violation‐related indicators. Financial services companies only led in disclosing neutral social indicators, not bad or violation‐related ones, so leant towards greenwashing. Results also suggest that after the GRI clarifying materiality principle in 2016, financial services disclosure quality dropped further by de‐emphasising environmental without lifting social disclosures, while mining and metals' stayed unchanged. The results confirm and better specify widely indicated reporting weaknesses, contributing to content analysis methodology and legitimacy theory. This arms guideline setters, investors and other stakeholders to better evaluate/design reports and might encourage firms to voluntarily improve disclosures.
Plasma metabolomic profile associated with fatigue in cancer patients
Authors: Feng Li Rebekah , Barb Jennifer J. , Regan Jeniece , Saligan Leorey N.
Published: February 2021

Background

Metabolomics is the newest ‐omics methodology and allows for a functional snapshot of the biochemical activity and cellular state. The goal of this study is to characterize metabolomic profiles associated with cancer‐related fatigue, a debilitating symptom commonly reported by oncology patients.

Methods

Untargeted ultrahigh performance liquid chromatography/mass spectrometry metabolomics approach was used to identify metabolites in plasma samples collected from a total of 197 participants with or without cancer. Partial least squares‐discriminant analysis (PLS‐DA) was used to identify discriminant metabolite features, and diagnostic performance of selected classifiers was quantified using area under the receiver operating characteristics (AUROC) curve analysis. Pathway enrichment analysis was performed using Fisher's exact test and the Kyoto Encyclopedia of Genes and Genomes (KEGG) metabolic pathway database.

Findings

The global metabolomics approach yielded a total of 1120 compounds of known identity. Significant metabolic pathways unique to fatigued cancer versus control groups included sphingolipid metabolism, histidine metabolism, and cysteine and methionine metabolism. Significant pathways unique to non‐fatigued cancer versus control groups included inositol phosphate metabolism, primary bile acid biosynthesis, ascorbate and aldarate metabolism, starch and sucrose metabolism, and pentose and glucuronate interconversions. Pathways shared between the two comparisons included caffeine metabolism, tyrosine metabolism, steroid hormone biosynthesis, sulfur metabolism, and phenylalanine metabolism.

Conclusions

We found significant metabolomic profile differences associated with cancer‐related fatigue. By comparing metabolic signatures unique to fatigued cancer patients with metabolites associated with, but not unique to, fatigued cancer individuals (overlap pathways) and metabolites associated with cancer but not fatigue, we provided a broad view of the metabolic phenotype of cancer‐related fatigue.
Gingival Sculpting: A Simple Gingival Depigmentation Technique Using Bur Abrasion and Scalpel Combined – A Case Report
Authors: Kawar Nadia I. , Alrayyes Sahar M. , Khuzam Maher , Haddad Jacob R. , Tilwani Sunny K.
Published: February 2021

Introduction

Dentofacial esthetics demands have increased tremendously in the past decade. Psychological impact of unsatisfactory esthetic appearance can manifest in decreased sense of self‐esteem and can negatively affect social and professional interactions. Esthetic awareness of dental patients has extended to include requests of gingival color modification. Gingival pigmentation can be physiological due to ethnic pigmentation or can be a result of various pathological processes. Different surgical modalities, tools and materials have been used in management of gingival pigmentation. This case report is introducing a simple, cost effective, minimally invasive technique of gingival sculpting for the purpose of significantly reducing gingival pigmentation.

Case Presentation

A healthy 32‐year‐old male patient presented with a chief complaint of gingival pigmentation that is causing him distress and low self‐esteem. Gingival sculpting technique was used. This simple technique uses a combination of two methods, bur abrasion and scalpel blade with copious irrigation. The procedure resulted in minimal intra and postoperative complications and excellent esthetic results achieved instantly and maintained at 3 months postoperatively. High patient esthetic satisfaction was achieved.

Conclusion

Gingival sculpting is minimally invasive procedure that can be performed at any dental office. It renders excellent esthetic results using minimal chair time and down time for the patient. It is well tolerated by the patient with minimal bleeding, postoperative pain, and rapid healing time. Long‐term follow‐up is needed to ensure stability and lack of recurrence.
Advocating for your child in the digital age
Authors: Knopf Alison
Published: February 2021

Chances are therapy is being delivered using digital health tools in the pandemic. Last year the American Academy of Child and Adolescent Psychiatry (AACAP) issued some guidance for parents on how to work with psychiatrists in the digital age.
Modified wire atrial septostomy with a reverse transseptal puncture in an infant: Case report
Authors: Nagatomo Yusaku , Nagata Hazumu , Yamamura Kenichiro , Ohga Shouichi
Published: February 2021

We report a modified technique of wire atrial septostomy (WAS) with a reverse transseptal puncture (TSP) in an infant case of pulmonary atresia with intact ventricular septum. A radiofrequency (RF) wire was advanced to the septum through a 4 Fr pigtail catheter hooked on the left side of atrial septum and RF energy was applied while advancing the wire across the septum. Following that reverse TSP, WAS was performed to cut the septal tissue using a 0.010 microwire and RF wire. The atrial septum defect (ASD) was enlarged to a size of 15 mm. WAS with a reverse TSP could be a useful and safe method to enlarge ASD in infants with congenital heart diseases.
Case Report of a 23‐year‐old first gravida presenting with breathlessness and oxygen saturation of 80%
Authors: Porsche Raphael , Höhn René , Krüger Kirsten , Kalbhenn Johannes , Bansbach Joachim
Published: February 2021

Central principles are interdisciplinary teamwork and keeping the ratio between pulmonary vascular resistance (PVR) and systemic vascular resistance (SVR) balanced to avoid vicious circle with right heart failure and hypoxia.
A case of antisynthetase syndrome with chilblains‐like lesions and microangiopathy
Authors: Abrassart Tom , Roland Thomas , Laurent France , Rossi Camelia
Published: February 2021

We present the case of a 50‐year‐old woman with febrile myalgia, chilblains‐like lesions, and cough. Antinuclear antibodies and anti‐PL‐12 antisynthetase autoantibodies were found in complementary examinations. Interstitial lung disease was found on chest computed tomography. Nailfold capillaroscopy showed microangiopathic lesions.

Antisynthetase syndrome is a recently described entity in inflammatory myopathies, with specific clinical criteria. Interstitial lung disease is very common, especially in anti‐PL‐12 associated antisynthetase syndrome. Raynaud's phenomenon is another well‐defined criterion. However, microangiopathic damage is probably underestimated and the role of nailfold capillaroscopy in the diagnosis has not been established yet.
A rare noncancerous but life‐threatening tumor in urinary bladder
Authors: Wang Chien‐Sheng , Guu Shiao‐Jin , Wang Chii‐Jye , Yang Sheau‐Fang , Ke Hung‐Lung , Lee Yung‐Chin , Jhan Jhen‐Hao
Published: February 2021

IMT is a rare but sometimes life‐threatening tumor. Although presenting with muscle invasion, local surgical resection with TURBT and close follow‐up are adequate with bladder function and life quality preservation compared to partial cystectomy.
Atypical solid pseudopapillary tumor of the pancreas in a 14‐year‐old
Authors: Meriam Sabbah , Ines Briki , Fatma Ben Farhat , Fatma Khanchel , Dhafer Haddad , Imen Helal , Nawel Bellil , Chiraz Chammakhi , Dalila Gargouri
Published: February 2021

Diagnostic approach can be difficult in pediatric pancreatic masses. Our case shows that even though radiologic appearance was not conclusive, surgery remains the main treatment in resectable masses especially in children.
Metallic Ag Confined on SnO2 Surface for Soot Combustion: the Influence of Ag Distribution and Dispersion on the Reactivity
Authors: Feng Xiaohui , Zhang Shijing , Wang Fumin , Ma Jun , Xu Xianglan , Lai Qiang , Xu Junwei , Fang Xiuzhong , Wang Xiang
Published: February 2021

To unravel the surface confinement effect of SnO2 for Ag, and find an effective way to design practical soot combustion catalysts, an XRD extrapolation method has been adopted for the first time to analyze the distribution and dispersion of metallic Ag on SnO2 surface. Ag addition can generate more surface oxygen vacancies on SnO2, thus forming richer amount of surface O2− and O22− anions. However, the amount of soot reactive oxygen sites is significantly influenced by the distribution of Ag. It is quantified that 1.86 mmol Ag/100 m2 SnO2 surface, which is equal to 5.2 wt% loading, is a threshold value for Ag distribution. Below the threshold, Ag is nearly in amorphous state, and has strong interaction with the SnO2 support, thus producing more soot reactive surface oxygen sites. Furthermore, the redox property of SnO2 lattice oxygen is enhanced by Ag addition. Therefore, metallic Ag in nearly amorphous state plays a critical role for the reaction. Ag crystallites formed on the surface above the threshold have negative influence on the activity. The best Ag/SnO2 catalyst can be fabricated by loading the threshold amount of Ag over SnO2 surface to get the maximum quantity of amorphous Ag species.
Selection of State Equation and Innovative Process Design for Removing CO2 by Azeotropic Distillation
Authors: Wang Haiqin , Wang Ce , Zhang Zubin , Fan Minglong , Yan Xiaodong , Li Fengqi
Published: February 2021

A thermodynamic consistency test was performed on the gas‐liquid equilibrium data of three binary mixtures, namely, CH4‐C2H6, CH4‐CO2, and C2H6‐CO2, measured by Wei and Brown at three different temperatures to verify the reliability of the data. Peng‐Robinson (PR), Redlich‐Kwong (RK), and Soave‐Redlich‐Kwong (SRK) equations of state combined with Margles mixing rules were used to fit the gas‐liquid equilibrium data of these three models. The results indicate that the PR‐Margles mixed model can make the average absolute deviation of test data and calculated data pressure and vapor fraction less than 0.19 and 0.0025, respectively, which is superior to RK‐Margles and SRK‐Margles mixed models. Finally, an azeotropic distillation method with C2H6 as entrainer for removing CO2 from natural gas was explored and optimized.
Production of High‐Purity Hydrogen and Layered Doubled Hydroxide by Hydrolysis of Mg‐Al Alloys
Authors: Zheng Tong , Zhang Jingqi , Tang Yang , Wan Pingyu , Yuan Qipeng , Hu Hanjun , Coulon Frederic , Hu Qing , Yang Xiao Jin
Published: February 2021

Hydrogen is becoming an important clean energy and layered doubled hydroxide (LDH) is of great interest for many applications, including water treatment, environmental remediation, and chemical catalysis. The production of high‐purity hydrogen and LDH by the hydrolysis of Mg‐Al alloys is reported. The effects of initial pH, reaction temperature, reaction time, and alloy's Mg/Al mass ratio on the rate of hydrogen generation and the purity of LDH are evaluated and the solid hydrolysis products are characterized by different techniques. The initial rate of hydrogen generation increases with decreasing initial pH and increasing reaction temperature and Mg/Al ratio while the purity of LDH increases with Mg/Al ratio, reaction temperature and time. This study may provide a new, green, and sustainable approach for storage of hydrogen and material for water treatment.
Preparation of Highly Pyrrolic‐Nitrogen‐Doped Carbon Aerogels for Lithium‐Sulfur Batteries
Authors: Zhang Meng , Lu Chunxiang , Bi Zhihong , Xu Xiaolu , Ren Xiaodan , Li Xinzhi , Lu Kuan , Yuan Shuxia
Published: February 2021

A cellulose‐based, highly pyrrolic‐nitrogen‐doped carbon aerogel (PNCA) was successfully prepared by using a facile and ecofriendly in situ dissolution process; the resulting aerogel had a honeycomb‐like three‐dimensional structure and a highly pyrrole‐nitrogen‐doped configuration. As the host material of the cathode in lithium‐sulfur batteries, PNCA achieved a high sulfur loading up to 76.7 %, owing to the distribution of pyrrole nitrogen and the three‐dimensional network structure. As a consequence, this composite cathode exhibits outstanding electrochemical performance, including long‐term cycling stability (1292.8 mA h g−1 at 0.2 C over 500 cycles and 540.5 mA h g−1 at 1 C over 1000cycles) and excellent rate performance (1249.9 mA h g−1 at 0.2 C, 1060 mA h g−1 at 0.5 C, 936.3 mA h g−1 at 1 C, and 698 mA h g−1 at 3 C remained). This study aims at providing new insights for the synthesis of highly reactive nitrogen‐doped carbon materials and then further proposing a future viewpoint on the design and development of advanced host materials for lithium‐sulfur batteries. Furthermore, the key mechanism of the pyrrole‐doped nitrogen configuration in the catalytic conversion of polysulfides was revealed for the first time after being combined with DFT theoretical calculations.
Ultrafast Dynamics and Photoresponse of a Fungi‐Derived Pigment Xylindein from Solution to Thin Films
Authors: Krueger Taylor D. , Giesbers Gregory , Van Court Ray C. , Zhu Liangdong , Kim Ryan , Beaudry Christopher M. , Robinson Seri C. , Ostroverkhova Oksana , Fang Chong
Published: February 2021

Organic semiconductor materials have recently gained momentum due to their non‐toxicity, low cost, and sustainability. Xylindein is a remarkably photostable pigment secreted by fungi that grow on decaying wood, and its relatively strong electronic performance is enabled by π–π stacking and hydrogen‐bonding network that promote charge transport. Herein, femtosecond transient absorption spectroscopy with a near‐IR probe was used to unveil a rapid excited‐state intramolecular proton transfer reaction. Conformational motions potentially lead to a conical intersection that quenches fluorescence in the monomeric state. In concentrated solutions, nascent aggregates exhibit a faster excited state lifetime due to excimer formation, confirmed by the excimer→charge‐transfer excited‐state absorption band of the xylindein thin film, thus limiting its optoelectronic performance. Therefore, extending the xylindein sidechains with branched alkyl groups may hinder the excimer formation and improve optoelectronic properties of naturally derived materials.
Zinc Oxide Defect Microstructure and Surface Chemistry Derived from Oxidation of Metallic Zinc. Thin Film Transistor and Sensoric Behaviour of ZnO Films and Rods
Authors: Hoffmann Rudolf C. , Sanctis Shawn , Liedke Maciej O. , Butterling Maik , Wagner Andreas , Njel Christian , Schneider Jörg J.
Published: February 2021

Invited for the cover of this issue is Jörg J. Schneider and co‐workers at Technical University Darmstadt, Helmholtz‐Zentrum Dresden‐Rossendorf and KIT Karlsruhe. The image depicts the application of high energy generated electron/positron couples which are able to detect defects sites in semiconducting zinc oxide thin films. Read the full text of the article at 10.1002/chem.202004270.
The Missing Parent Compound [(C5H5)Fe(η5‐P5)]: Synthesis, Characterization, Coordination Behavior and Encapsulation
Authors: Heinl Claudia , Peresypkina Eugenia , Balázs Gábor , Mädl Eric , Virovets Alexander V. , Scheer Manfred
Published: February 2021

The so far missing parent compound of the large family of pentaphosphaferrocenes [CpFe(η5‐P5)] (1 b) was synthesized by the thermolysis of [CpFe(CO)2]2 with P4 using the very high‐boiling solvent diisopropylbenzene. It was comprehensively characterized by, inter alia, NMR spectroscopy, single crystal X‐ray structure analysis, cyclic voltammetry and DFT computations. Moreover, its coordination behavior towards CuI halides was explored, revealing the unprecedented 2D polymeric networks [{CpFe(η5:1:1:1:1‐P5)}Cu2(μ‐X)2]n (2 a: X=Cl, 2 b: X=Br) and [{CpFe(η5:1:1‐P5)}Cu(μ‐I)]n (3) and even the first cyclo‐P5‐containing 3D coordination polymer [{CpFe(η5:1:1‐P5)}Cu(μ‐I)]n (4). The sandwich complex 1 b can also be incorporated in nano‐sized supramolecules based on [Cp*Fe(η5‐P5)] (1 a) and CuX (X=Cl, Br, I): [CpFe(η5‐P5)]@[{Cp*Fe(η5‐P5)}12(CuX)20‐n] (5 a: X=Cl, n=2.4; 5 b: X=Br, n=2.4; 5 c: X=I, n=0.95). Thereby, the formation of the CuI‐containing fullerene‐like sphere 5 c is found for the first time.
Hierarchical Spin‐Crossover Cooperativity in Hybrid 1D Chains of FeII‐1,2,4‐Triazole Trimers Linked by [Au(CN)2]− Bridges
Authors: Ezzedinloo Lida , Zenere Katrina A. , Xie Zixi , Ahmed Manan , Scottwell SynØve , Bhadbhade Mohan , Brand Helen E. A. , Clegg Jack K. , Hua Carol , Sciortino Natasha F. , Parker Lachlan C. , Powell Benjamin J. , Kepert Cameron J. , Neville Suzanne M.
Published: February 2021

Foremost, practical applications of spin‐crossover (SCO) materials require control of the nature of the spin‐state coupling. In existing SCO materials, there is a single, well‐defined dimensionality relevant to the switching behavior. A new material, consisting of 1,2,4‐triazole‐based trimers coordinated into 1D chains by [Au(CN)2]− and spaced by anions and exchangeable guests, underwent SCO defined by elastic coupling across multiple dimensional hierarchies. Detailed structural, vibrational, and theoretical studies conclusively confirmed that intra‐trimer coupling was an order of magnitude greater than the intramolecular coupling, which was an order of magnitude greater than intermolecular coupling. As such, a clear hierarchy on the nature of elastic coupling in SCO materials was ascertained for the first time, which is a necessary step for the technological development of molecular switching materials.
Renewable Hydrogen: Modular Concepts from Production over Storage to the Consumer
Authors: Trattner Alexander , Höglinger Martin , Macherhammer Marie‐Gabrielle , Sartory Markus
Published: February 2021

A simulation tool called HYDRA to optimize individual hydrogen infrastructure layouts is presented. The different electrolyzer technologies, namely proton exchange membrane electrolysis, anion exchange membrane electrolysis, alkaline electrolysis, and solid oxide electrolysis, as well as hydrogen storage possibilities are described in more detail and evaluated. To illustrate the application opportunities of HYDRA, three project examples are discussed. The examples include central and decentral applications while taking the usage of hydrogen into account.
Experimentelle Escape Box
Authors: Strippel Christian Georg , Philipp Schröder Thomas , Sommer Katrin
Published: February 2021

Escape Rooms erfreuen sich wachsender Beliebtheit. Der Einsatz der Escape Box ermöglicht die Übertragung des Spielprinzips auf elektrochemische Experimente rund um galvanische Elemente im Chemieunterricht und die Bearbeitung der Box an sich im fächerverbindenden (Projekt‐)Unterricht. In der Escape Box werden über einen Microcontroller ein einfaches Voltmeter, ein LCD und ein Servo verbunden und über ein Programm angesteuert. Dieser Mechanismus ermöglicht ein spannungsinduziertes Öffnen und Schließen der Box. Die Spannung kann über verschiedene galvanische Elemente erzeugt werden. Alle Teile der Box sind so ausgelegt, dass die mechanische, elektrotechnische und chemische Funktionsweise transparent und nachvollziehbar ist. So ermöglicht ihr Einsatz eine produktorientierte Verbindung von Chemie, Technik und Informatik.
Study on the cracking of carbon anodes used in aluminium industry
Authors: Amrani Salah , Kocaefe Duygu , Kocaefe Yasar , Bhattacharyay Dipankar , Bouazara Mohamed , Côté Jules
Published: February 2021

Carbon anodes are used in aluminium electrolysis. Their quality plays a major role in the stability of cell operation and energy consumption. The improvement of the quality of carbon anodes is essential to respond to the many challenges the aluminium industry is facing with respect to issues related to carbon loss, energy use, cell performance, and production cost, especially for high amperage cells. The presence of cracks increases the anode resistivity, and, as a result, power consumption, production cost, and greenhouse gas emissions also increase. Therefore, it is important to know how the cracks form during anode production. An industrial measurement campaign was carried out at the Aluminerie Alouette Inc. (AAI) plant in Sept‐Îles, Québec, Canada. The effect of raw materials (type of coke, pitch, and butts), vibro‐compaction (vibro‐compactor type, balloon pressure, and vibration time), and the position of anodes in the baking furnace on anode cracking was investigated. It was found that the anode centre is the region that contains the most cracks compared to other parts of the anode. The cracks in the horizontal direction are more predominant than those in other directions. The raw materials and the operating parameters of each anode production step affect anode cracking.
Methods of coating ceramic supports with carbon and Ni‐based catalytically active formulations
Authors: Achouri Inès E. , Chaouki Jamal , Abatzoglou Nicolas
Published: February 2021

Nickel‐based catalysts have been widely investigated as they exhibit high activity for reforming reactions, particularly in order to produce syngas. Microwave‐assisted heating is gaining interest as an energy‐efficient heating solution for heterogenous catalytic reactions, and for its exciting prospects related to selective catalyst heating. The objective of this study is to partially or completely coat a fluidizable support with a carbon layer to enhance the support surface reactivity to microwaves, then deposit Ni/Al active species on the carbon‐coated silica surface. This configuration would provide a fine distribution of the catalyst on the surface and an enhanced heating performance with microwaves due to the presence of carbon. The following three synthesis methods have been studied: (a) plasma deposition, (b) hydrothermal synthesis, and (c) coating with organic compounds. The resultant materials have been characterized using scanning electron microscopy with energy dispersive x‐ray spectroscopy (SEM‐EDXS); specific surface area was determined using the multipoint Brunauer, Emmett, and Teller (BET) method and elemental analysis for carbon quantification. The results show that the type of carbon deposited on the surface depends on the preparation method and that the latter is a factor influencing the active particle's deposition. Coating with organic compounds has proven to be the method that provides the best deposition of the active phase, while the hydrothermal technique shows the best carbon surface adherence.
Phosphinic Acid/NaI Mediated Reductive Cyclization Approach for Accessing the L‐1‐Deoxynojirimycin Using a Two‐Component Three‐Centered (2C3C) Ugi Type Reaction
Authors: Azad Chandra S , Shukla Pratibha , Olson Mark A , Narula Anudeep K
Published: February 2021

Main observation and conclusion

A catalytic two‐component three‐centered (2C3C) Ugi‐type reaction was developed for the synthesis of L‐1‐deoxynojirimycin (DNJ) isomers using a chiron approach. This new and quite mild catalytic system, comprised of phenylphosphinic acid/NaI, was used to synthesize both the L‐allo‐DNJ and L‐altro‐DNJ in high yield.
Electrochemical Analysis for Multiscale Single Entities on the Confined Interface†
Authors: Zhao Haipei , Ma Jinliang , Zuo Xiaolei , Li Fan
Published: February 2021

Single entities detection reveals heterogeneity and random processes hidden in ensemble measurements. Obtaining accurate single‐entity information is challenging. The electrochemical analysis is at high spatial resolution and high temporal resolution to analyze single entities and measure the fast kinetics process. In this minireview, we will focus on the electrochemical strategies for single multiscale entities.
Impact of anemia on clinical outcomes of patients with atrial fibrillation: The COOL‐AF registry
Authors: Krittayaphong Rungroj , Pumprueg Satchana , Thongsri Tomon , Wiwatworapan Weerapan , Choochunklin Thaworn , Kaewkumdee Pontawee , Yindeengam Ahthit ,   for the COOL‐AF Investigators
Published: February 2021

Background

To determine whether anemia is an independent risk factor for ischemic stroke and major bleeding in patients with non‐valvular atrial fibrillation (NVAF).

Hypothesis

Anemia in patients with NVAF increase risk of clinical complications related to atrial fibrillation.

Methods

We conducted a prospective multicenter registry of patients with NVAF in Thailand. Demographic data, medical history, comorbid conditions, laboratory data, and medications were collected and recorded, and patients were followed‐up every 6 months. The outcome measurements were ischemic stroke or transient ischemic attack (TIA), major bleeding, heart failure (HF), and death. All events were adjudicated by the study team. We analyzed whether anemia is a risk factor for clinical outcomes with and without adjusting for confounders.

Results

There were a total of 1562 patients. The average age of subjects was 68.3 ± 11.5 years, and 57.7% were male. The mean hemoglobin level was 13.2 ± 1.8 g/dL. Anemia was demonstrated in 518 (33.16%) patients. The average follow‐up duration was 25.8 ± 10.5 months. The rate of ischemic stroke/TIA, major bleeding, HF, and death was 2.9%, 4.9%, 1.8%, 8.6%, and 9.2%, respectively. Anemia significantly increased the risk of these outcomes with a hazard ratio of 2.2, 3.2, 2.9, 1.9, and 2.8, respectively. Oral anticoagulants (OAC) was prescribed in 74.8%; warfarin accounts for 89.9% of OAC. After adjusting for potential confounders, anemia remained a significant predictor of major bleeding, heart failure, and death, but not for ischemic stroke/TIA.

Conclusion

Anemia was found to be an independent risk factor for major bleeding, heart failure, and death in patients with NVAF.
Synthesis of Carboxamide‐Containing Tranylcypromine Analogues as LSD1 (KDM1A) Inhibitors Targeting Acute Myeloid Leukemia
Authors: Teresa Borrello Maria , Benelkebir Hanae , Lee Adam , Hin Tam Chak , Shafat Manar , Rushworth Stuart A. , Bowles Kristian M. , Douglas Leon , Duriez Patrick J. , Bailey Sarah , Crabb Simon J. , Packham Graham , Ganesan A.
Published: February 2021

Lysine‐specific demethylase 1 (LSD1/KDM1A) oxidatively removes methyl groups from histone proteins, and its aberrant activity has been correlated with cancers including acute myeloid leukemia (AML). We report a novel series of tranylcypromine analogues with a carboxamide at the 4‐position of the aryl ring. These compounds, such as 5 a and 5 b with benzyl and phenethylamide substituents, respectively, had potent sub‐micromolar IC50 values for the inhibition of LSD1 as well as cell proliferation in a panel of AML cell lines. The dose‐dependent increase in cellular expression levels of H3K4me2, CD86, CD11b and CD14 supported a mechanism involving LSD1 inhibition. The tert‐butyl and ethyl carbamate derivatives of these tranylcypromines, although inactive in LSD1 inhibition, were of similar potency in cell‐based assays with a more rapid onset of action. This suggests that carbamates can act as metabolically labile tranylcypromine prodrugs with superior pharmacokinetics.
Design, Synthesis and Biological Activity of New Amides Derived from 3‐Benzhydryl and 3‐sec‐Butyl‐2,5‐dioxo‐pyrrolidin‐1‐yl‐acetic Acid
Authors: Góra Małgorzata , Czopek Anna , Rapacz Anna , Giza Agnieszka , Koczurkiewicz‐Adamczyk Paulina , Pękala Elżbieta , Obniska Jolanta , Kamiński Krzysztof
Published: February 2021

The aim of this study was to design and synthesize two new series of pyrrolidine‐2,5‐dione‐acetamides with a benzhydryl or sec‐butyl group at position 3 as potential anticonvulsants. Their anticonvulsant activity was evaluated in standard animal models of epilepsy: the maximal electroshock (MES), the 6 Hz, and the subcutaneous pentylenetetrazole (scPTZ) tests. The in vivo studies revealed the most potent anticonvulsant activity for 15 (3‐(sec‐butyl)‐1‐(2‐(4‐(3‐trifluoromethylphenyl)piperazin‐1‐yl)‐2‐oxoethyl)pyrrolidine‐2,5‐dione), with ED50 values of 80.38 mg/kg (MES) and 108.80 mg/kg (6 Hz). The plausible mechanism of action was assessed in in vitro binding assays, in which 15 interacted effectively with voltage‐gated sodium (site 2) and L‐type calcium channels at a concentration of 100 μM. Subsequently, the antinociceptive activity of compounds 7 and 15 was observed in the hot plate test of acute pain. Moreover, compounds 7, 11 and 15 demonstrated an analgesic effect in the formalin test of tonic pain. The hepatotoxic properties of the most effective compounds (7, 11 and 15) in HepG2 cells were also investigated.
In Silico Tandem Mass Spectrometer: an Analytical and Fundamental Tool
Authors: Carrà Andrea , Spezia Riccardo
Published: February 2021

In this article, we summarize some aspects of the recently developed computational approach to model and predict collision induced dissociation mass spectra. In particular, we describe how initial conditions can be set to model fragmentation conditions and then obtain different results from the analysis of an ensemble of reactive trajectories. This approach was studied and validated on different systems, from small organic molecules to large biomolecules. Recently an iterative procedure was proposed to increase the fragmentation sampling, reducing computational time and providing a more comprehensive fragmentation pattern. All these fundamental developments are at the basis of the application of this approach to analytical problems. One important and possible outcome will be in creating an in silico data base which will be an useful complement to the experimental ones. This is discussed within other possible future outlooks.