bluuebunny/crossref_metadata_2025 huggingface dataset:
Preparation of Distant Quaternary Carbon Stereocenters by Double Selective Ring‐Opening of 1,1‐Biscyclopropyl Methanol Derivatives
Authors: Siddaraju Yogesh , Sabbatani Juliette , Cohen Anthony , Marek Ilan
Published: May 2022

The diastereoselective double carbometalation reaction of cyclopropenes provides, in a single‐pot operation, two ω‐ene‐[1,1]‐bicyclopropyl ester derivatives. One regioisomer then undergoes a Pd‐catalyzed addition of aryl iodide to provide skipped dienes possessing several distant stereocenters including two congested quaternary carbon centers with excellent diastereoselectivity.
PdFe Single‐Atom Alloy Metallene for N2 Electroreduction
Authors: Li Xingchuan , Shen Peng , Luo Yaojing , Li Yunhe , Guo Yali , Zhang Hu , Chu Ke
Published: May 2022

Single‐atom alloys hold great promise for electrocatalytic nitrogen reduction reaction (NRR), while the comprehensive experimental/theoretical investigations of SAAs for the NRR are still missing. Herein, PdFe1 single‐atom alloy metallene, in which the Fe single atoms are confined on a Pd metallene support, is first developed as an effective and robust NRR electrocatalyst, delivering exceptional NRR performance with an NH3 yield of 111.9 μg h−1 mg−1, a Faradaic efficiency of 37.8 % at −0.2 V (RHE), as well as a long‐term stability for 100 h electrolysis. In‐depth mechanistic investigations by theoretical computations and operando X‐ray absorption/Raman spectroscopy indentify Pd‐coordinated Fe single atoms as active centers to enable efficient N2 activation via N2‐to‐Fe σ‐donation, reduced protonation energy barriers, suppressed hydrogen evolution and excellent thermodynamic stability, thus accounting for the high activity, selectivity and stability of PdFe1 for the NRR.
Atomically Dispersed Janus Nickel Sites on Red Phosphorus for Photocatalytic Overall Water Splitting
Authors: Wang Menglong , Xu Shuai , Zhou Zhaohui , Dong Chung‐Li , Guo Xu , Chen Jeng‐Lung , Huang Yu‐Cheng , Shen Shaohua , Chen Yubin , Guo Liejin , Burda Clemens
Published: May 2022

Single‐atom nickel catalysts hold great promise for photocatalytic water splitting due to their plentiful active sites and cost‐effectiveness. Herein, we adopt a reactive‐group guided strategy to prepare atomically dispersed nickel catalysts on red phosphorus. The hydrothermal treatment of red phosphorus leads to the formation of P−H and P−OH groups, which behave as the reactive functionalities to generate the dual structure of single‐atom P−Ni and P−O−Ni catalytic sites. The produced single‐atom sites provide two different functions: P−Ni for water reduction and P−O−Ni for water oxidation. Benefitting from this specific Janus structure, Ni‐red phosphorus shows an elevated hydrogen evolution rate compared to Ni nanoparticle‐modified red phosphorus under visible‐light irradiation. The hydrogen evolution rate was additionally enhanced with increased reaction temperature, reaching 91.51 μmol h−1 at 70 °C, corresponding to an apparent quantum efficiency of 8.9 % at 420 nm excitation wavelength.
Palladium hetero‐di(N‐heterocyclic carbene) complexes and their catalytic activities in direct C–H arylation of heteroarenes
Authors: Ghatak Kausani , Huynh Han Vinh
Published: May 2022

A library of neutral and cationic palladium complexes of cis‐chelating hetero‐dicarbene ligands have been prepared. These ligands contain two different NHC donors allowing for a wider degree of variation, and the impact of the distinct NHC units has been compared using various spectroscopic means. In addition, the catalytic activities of these complexes in the direct C‐H arylation of thiophenes with aryl halides were studied leading to the finding that the neutral dibromido complexes of the type [PdBr2(diNHC)] generally outperformed their cationic [Pd (NCMe)2(diNHC)](OTf)2 counterparts. More importantly, complexes containing more distinct NHC units give rise to superior catalysts due to an amplified “stereoelectronic asymmetry” within the complex. A preliminary photophysical study of some selected thiophene reaction products has been conducted as well. The ability to individually change each NHC donor in such dicarbene ligands allows for a better fine‐tuning of complex properties in search for superior catalysts.
Reusable water‐soluble homogeneous catalyst in aqueous‐phase transfer hydrogenation of N‐heteroarenes with formic acid: Uracil‐based bifunctional Ir‐NHC catalyst is the key
Authors: Maji Babulal , Choudhury Joyanta
Published: May 2022

Transfer hydrogenation of N‐heteroarenes was successfully achieved using a water‐soluble half‐sandwich Cp*Ir‐based catalyst containing a uracil‐based bifunctional abnormal NHC ligand, using HCOOH/HCOONa buffer solution as the hydrogen source. Reduction of N‐heteroarenes was shown to be highly pH‐dependent, and an acidic pH = 3.0 was found to be suitable for the best activity. The catalyst showed excellent functional group compatibility and high turnover number (up to 10,400), with catalyst loadings as low as 0.005 mol%. Finally, we demonstrated the catalyst's efficacy and applicability toward reusable and repetitive transfer hydrogenation using liquid/liquid extraction methodology, which underscored the significance of sustainable usage of noble metal catalysts in such transformations.
Transferable shadow cure: A new approach to achieving cationic photopolymerization in light‐restricted areas
Authors: Schissel Sage M. , Jessop Julie L. P.
Published: May 2022

Transferable shadow cure is presented as an improved method of shadow cure. In this new method, active centers are formed in one space, and active‐center‐containing monomer is then moved to another space where the bulk of the polymerization proceeds. This transference enables inclusion of pigments and fillers, layering in thick systems, and polymerization in complex geometries. Kinetic analysis of shadow‐cure samples shows conversions consistently ~15% less than comparable light‐cure samples. In addition, shadow‐cure films have a higher Tg and crosslink density than light‐cure films, likely driven by annealing that occurs during the first dynamic mechanical analyzer temperature ramp sequence. A central‐composite design explored the effect of sample depth, effective irradiance, exposure area, and exposure time on conversion and the weight percent of the light‐cure section. The model predicts both responses are maximized by increasing effective irradiance and exposure time and decreasing sample depth, which is consistent with classical photopolymerization kinetics.
Implicit discrete‐time fast terminal sliding mode control with disturbance compensation
Authors: Wang Cong , Xia Hongwei , Wang Yanmin , Ren Shunqing
Published: May 2022

In this paper, an implicit discrete‐time fast terminal sliding mode (DFTSM) control with disturbance compensation is designed and analyzed for uncertain high‐order systems. First, a recursive discrete sliding surface is constructed based on implicit Euler technique, which can completely eliminate discretization chattering so as to significantly reduce the boundary layer of sliding mode motion. With the help of a high‐order disturbance compensator, the accuracy limitation of implicit DFTSM control systems is overcome by increasing the order of sliding mode. Then the finite‐time convergence of implicit DFTSM is proved for the first time, and the influence relationship of control parameters on the convergence speed and control accuracy of the algorithm is established. Finally, two numerical examples are provided to demonstrate the effectiveness and superiority of the proposed design approach.
Speed control strategy of dual flexible servo system considering time‐varying parameters for flexible manipulator with an axially translating arm
Authors: Shang Dongyang , Li Xiaopeng , Yin Meng , Li Fanjie
Published: May 2022

Many factors lead to fluctuations of output speed in the motor side during the movement processes in a flexible manipulator with an axially translating arm. These factors include the time‐varying characteristics of manipulator parameters, external disturbance, and flexibility in the manipulator. The vibration of flexible manipulators is strengthened by fluctuations of output speed, which seriously affects the motion accuracy. Therefore, a variable parameters proportional–integral (PI) control strategy based on disturbance observer is adopted to reduce fluctuations of output speed in a dual flexible servo system. First, the dynamic model of the dual flexible servo system is established by the assumed mode method. Then, the variable parameters PI control strategy is applied to the servo system, and the controller parameters in different conditions are selected by pole placement strategies. Finally, numerical simulations and control experiments of the servo system are carried out. The results show that the control strategy using the variable parameters and disturbance observer could reduce fluctuations of output speed and improve the motion accuracy of flexible manipulators.
Developing a consensus statement for psychosocial support in active surveillance for prostate cancer
Authors: Beckmann Kerri , Cahill Declan , Brown Christian , Van Hemelrijck Mieke , Kinsella Netty
Published: May 2022

Purpose

Our objective was to prioritise the psychosocial support needs of men on active surveillance for prostate cancer and to develop a consensus statement to provide guidance on best practice psychosocial support for men choosing active surveillance and their families.

Subjects and methods

We undertook a patient and public involvement Delphi process over two rounds, informed by qualitative data and a comprehensive literature review, to prioritise the information and support needs of men on active surveillance for prostate cancer. Two panels were surveyed, a patient/carer panel (n = 55) and a health care provider panel (n = 114). Based on the findings of the Delphi surveys, an expert active surveillance discussion group developed a consensus statement to guide best practice.

Results

Patients and health care professionals differed slightly in their ideas concerning priorities for active surveillance psychosocial support. Broadly, agreed priority areas included ‐patients being involved in decision‐making, continuity of care, more streamlined access to health care teams, improved understanding of the risk of prostate cancer progression and information and support provided through both health care professionals and peers. Based on the identified priorities, the expert discussion group agreed on 22 consensus statements for best practice in psychosocial care for active surveillance in respect of (1) principles of an active surveillance programme; (2) structure of consultations; (3) content of information and support; and (4) delivery of information.

Conclusion

This consensus statement provides a framework for patient‐focused psychosocial support, which, if adopted, should increase uptake and adherence to active surveillance among men with prostate cancer.
Two spectroscopic methods for estimation of anti‐migraine medications: Sumatriptan and Zolmitriptan based on nucleophilic substitution reaction
Authors: Abo El Abass Samah , Abo Zaid Mona H. , El‐Enany Nahed , Aly Fatma
Published: May 2022

Sensitive and selective spectrophotometric and spectrofluorimetric methods have been developed for the estimation of two anti‐migraine drugs, namely sumatriptan succinate (SUM) and zolmitriptan (ZOL). These methods depend on producing a yellow‐coloured product after the reaction of the two drugs with 7‐chloro‐4‐nitrobenz‐2‐oxa‐1,3‐diazole (NBD‐Cl). The reaction products exhibited maximum absorbance at 481 nm in borate buffer of pH 9 and fluorescence emission peak at 540 nm after excitation at 470 nm for the two drugs. The linear ranges were 5–60 μg/ml for SUM and 5–50 μg/ml for ZOL in the spectrophotometric method (Method I), whereas this was 0.4–4 μg/ml for SUM and 0.5–5 μg/ml for ZOL in the spectrofluorimetric method (Method II). The method validity was assessed according to International Council for Harmonisation (ICH) guidelines. Statistical analysis of the results obtained from the proposed and comparison methods confirmed that the proposed methods were highly accurate and precise. The suggested methods could be used for the determination of the mentioned drugs in both pure form and in tablets.
Relationship between tumor mutational burden, gene mutation status, and clinical characteristics in 340 cases of lung adenocarcinoma
Authors: Ma Kai , Huang Fengxiang , Wang Yin , Kang Yan , Wang Qilong , Tang Jiaqi , Sun Panfeng , Lou Jiaojiao , Qiao Ruiping , Si Jiming , Cao Jian , Miao Lijun
Published: May 2022

Tumor mutational burden (TMB) is an emerging predictive marker of response to immune checkpoint inhibitor therapies. We evaluated the correlation between clinical indicators and high‐throughput sequencing results and TMB in lung adenocarcinoma patients, with the aim of finding simpler and more economical factors as surrogate markers for TMB.

The medical records, next‐generation sequencing data, and immunohistochemistry results of 340 lung adenocarcinoma patients who were admitted to the First Affiliated Hospital of Zhengzhou University between 2019 and 2020 were collected. The mutated genes were screened for, and the obtained mutated genes were subjected to functional enrichment analysis using R software. A protein–protein interaction (PPI) network was also constructed, and significant modules in the network were identified. Gene Ontology (GO) analyses were performed for the core genes. Univariate and multivariate correlation analyses were performed to judge the correlation between gene mutations and TMB.

Genes with a junction mutation rate >1 were selected to construct PPI network and 13 high‐connection core genes were screened. The results of GO enrichment analysis showed that the biological processes related to mutant core genes mainly included mitotic cell cycle and cell aging. Subsequently, ATM (p = 0.006) and PIK3CA (p = 0.008) mutation positivity were identified by univariate and multivariate correlation analysis, while TP53 (p = 0.003) and EGFR (p = 0.008) mutation negativity were significantly associated with elevated TMB.

The results of this study demonstrate that ATM‐ and PIK3CA‐positive and EGFR‐negative mutation status are strongly associated with high levels of TMB and have the potential to be predictive biomarkers of response to immune checkpoint inhibitors in lung adenocarcinoma patients.
Case of impacted subglottic metallic foreign body removal without tracheostomy through an endotracheal tube
Authors: Kim Minju , Park Haechan , Kwon Seong Keun
Published: May 2022

A foreign body in the upper airway can cause serious morbidity and mortality, especially in pediatric patients. This case report describes an innovative way to remove an impacted foreign body distal to the vocal folds through an endotracheal tube without tracheostomy.
A very rare case of splenosis and acquired chronic non‐cirrhotic portal vein thrombosis with cavernous transformation
Authors: Kadyrova Aliya , Baudinov Iliar , Mamytova Elmira , Ibraimov Kubat , Arzykulov Tynarbek , Mamatov Sagynali , Vityala Yethindra , Tagaev Tugolbai
Published: May 2022

We present a clinical case of a young woman who underwent splenectomy for thrombocytopenic splenomegaly at the age of 7 years. An acute diagnostic picture of splenosis of the left epigastric region and chronic non‐cirrhotic portal vein thrombosis with cavernous transformation was found 20 years later.
X‐Ray‐Based Tomographic Imaging for the Investigation of Laminar Mixing in Capillaries
Authors: Schuler Julia , Herath Jakob , Kockmann Norbert
Published: May 2022

Micro‐computed tomography is a promising non‐invasive imaging technology that offers high spatial resolution without requiring optical access. This opens the opportunity to analyze concentration fields in mixing equipment in 3D. To demonstrate the potential of the methodology, laminar mixing in helically coiled capillaries is investigated by tracking the radial distribution of potassium iodide along the main flow direction. Dean flow can be observed in the helically coiled capillaries, which intensifies with Reynolds number and decreasing effect of gravity.
Sensitive Detection of Halides and Nitrate in Organic and Aqueous Solvents through Selective Halogen Bonding on TTF‐SAM‐Modified Platinum Electrodes
Authors: Hijazi Hussein , Levillain Eric , Schöllhorn Bernd , Fave Claire
Published: May 2022

Tetrathiafulvalene derivatives were chemisorbed on platinum electrodes. The electrochemical behavior and the stability of the resulting redox active self‐assembled monolayers in the presence of various anions was studied by cyclic voltammetry. The particularly stable modified electrodes showed a high sensitivity for the detection of halides and nitrate in aprotic and aqueous solvents.
Electrooxidation of Alcohols on Mixed Copper–Cobalt Hydroxycarbonates in Alkaline Solution
Authors: Braun Michael , Behrendt Gereon , Krebs Moritz L. , Dimitri Patricia , Kumar Piyush , Sanjuán Ignacio , Cychy Steffen , Brix Ann Cathrin , Morales Dulce M. , Hörlöck Jennifer , Hartke Bernd , Muhler Martin , Schuhmann Wolfgang , Behrens Malte , Andronescu Corina
Published: May 2022

Mixed Cu‐Co hydroxycarbonates of the type (Cu1–xCox)2CO3(OH)2 have been synthesized over the whole range of Cu‐Co substitution (0≤x≤1) by co‐precipitation and their electrocatalytic activity in the oxidation reactions of ethanol (EOR), ethylene glycol (EGOR) and glycerol (GOR) in alkaline environment was evaluated to retrieve composition–activity correlations. Generally, cobalt incorporation led to higher activities for the alcohol oxidation (AOR) compared to the Cu‐only material and the results are compared with the competing oxygen evolution reaction (OER). On the Cu‐Co hydroxycarbonates, the electrooxidation of vicinal alcohols such as glycerol and ethylene glycol requires lower overpotentials than EOR and OER. Cu leaching from the hydroxycarbonate structure was observed in the presence of vicinal alcohols. The impact of chemical and electrochemical leaching of copper from the catalysts has been studied. The chemically leached catalyst was found to show increased AOR activity compared to other hydroxycarbonates, enabling the formation of larger amounts of formic acid during GOR measured in a circular flow cell electrolyzer. The results highlight that Cu‐Co hydroxycarbonates can be used as precursors to generate electrocatalytically active materials from Cu‐Co hydroxycarbonates for the AOR in alkaline solution.
Luminescent Organic‐Inorganic Hybrid Metal Halides: An Emerging Class of Stimuli‐Responsive Materials
Authors: Wang Zeping , Huang Xiaoying
Published: May 2022

Luminescent organic‐inorganic metal halides (OIMHs) are well known as a new materials family in recent years. Novel materials and applications of luminescent OIMHs have been explored by changing either the organic component or the metal halide species. Thereinto, the stimuli‐responsive (SR) phenomena in OIMHs have drawn much attention recently, for not only their attractive application potential but also the helpfulness in understanding the stability of OIMHs to the external environment. Herein, the luminescent OIMHs that are sensitive to external stimuli including contact, pressure, mechanical grinding, light, heat, and gas molecules, are reviewed, with an emphasis on analyses of the structural change during the SR process. The applications of SR luminescent OIMHs in widespread fields, including gas sensing, information encryption, and rewritable luminescent paper are summarized. Finally, the challenges that deserve to be further explored in this research field are discussed, which provides certain guidance for the future study of SR luminescent OIMHs.
Organocatalyzed asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N‐2,2,2‐trifluoroethylisatin ketimines
Authors: Zhou Xiao‐Jian , Zhao Jian‐Qiang , Lai Yue‐Qin , You Yong , Wang Zhen‐Hua , Yuan Wei‐Cheng
Published: May 2022

A readily available chiral cyclohexanediamine‐derived bifunctional tertiary amine‐squaramide catalyst is more effective for the asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N‐2,2,2‐trifluoroethylisatin ketimines. A range of structurally diverse spiro‐fused polyheterocyclic compounds containing oxindole, pyrrolidine, and hydrobenzofuran motifs were smoothly obtained in excellent results (up to 99% yield, >20:1 dr in all cases and up to 99% ee). This method features high efficiency, mild reaction conditions, exquisite asymmetric induction, wide functional group tolerance, great potential for scale‐up synthesis, and attractive product diversification.
Who Established the First Law of Thermodynamics?
Authors: Mitrovic Jovan
Published: May 2022

The first law of thermodynamics is believed to have been developed almost simultaneously by Julius Robert Mayer and James Prescot Joule in the 1840s. However, a closer look at history shows that this notion is not tenable. James Watt had a clear vision of energy conversion and conservation. In his 1769 patent, he laid down the foundations for the first law of thermodynamics, which was published in 1774. Watt did not use ordinary language to express his thoughts, but rather drawings that visualized his ideas. In accordance with his understanding of the first law, he conceived the technology of the steam engine.
Recent advances in the approaches to recover rare earths and precious metals from E‐waste: A mini‐review
Authors: Paranjape Purva , Yadav Manishkumar D.
Published: May 2022

In the present day, with the rapid rate of advancements in technology, gadgets become obsolete very fast. The chase to keep up with the latest technologies diminishes the gadget's lifespan considerably. Consequently, they are discarded within a short time after their production, resulting in electronic waste (E‐waste) being the fastest growing waste stream globally, with an annual production rate of 2.44 million short tonnes. The metals present in such E‐waste provide several attractive properties, rendering them crucial in several applications as components of electronic and electrical devices. The major roadblock faced by mankind today is an effective technology with high recovery, low cost, and minimal environmental impact to recycle such electronic waste. In this mini‐review, we elucidate the various recycling routes for metal extraction from waste and recent advances in the same. We have attempted to highlight the recent trends adopted by various researchers to recycle and extract valuable metals and rare earths from E‐waste. Finally, the challenges and prospects in the extraction of rare earths and precious metals for E‐waste research have been clearly brought out and suggestions have been made for future work.
Tunable Liquid Crystal Alignment and Driving Mode on Lanthanum Aluminum Zirconium Zinc‐Oxide Thin Film Achieved by Convenient Brush‐Coating Method
Authors: Wook Lee Dong , Hyun Kim Dong , Young Oh Jin , Kim Dae‐Hyun , Liu Yang , Seo Dae‐Shik
Published: May 2022

Tunable liquid crystal (LC) alignment with twisted nematic (TN) and vertical alignment (VA) driving modes is achieved by a convenient brush‐coating method. The brush‐coating process combines film deposition and alignment treatment processes, and lanthanum aluminum zirconium zinc oxide (LaAlZrZnO) is used for the LC alignment layer. X‐ray photoelectron spectroscopy results confirm LaAlZrZnO film formation with fine optical transparency. Atomic force microscopy and line profile data indicate nano/micro surface structure with dense or directional morphologies induced by shear stresses according to film curing temperature. Low‐temperature‐cured films exhibit hydrophobic properties with low surface energy, whereas high‐temperature‐cured films show hydrophilicity with high surface energy. The geometric constraints and chemical affinities of the films induce homeotropic and homogeneous LC alignments on the surface according to the film curing temperature, respectively. The LC alignment state is verified by polarized optical microscopy and pretilt angle analysis. The brush‐coated LaAlZrZnO film demonstrates high thermal budget for advanced LC systems. The VA‐mode and TN‐mode LC cells based on the LaAlZrZnO film enable high electro‐optical performances and low power consumption. Therefore, the brush‐coating method is expected to be adoptable for next‐generation LC device applications.
Pharmacokinetics and Bioequivalence of Single‐Oral‐Dose Linagliptin: A Randomized, 2‐Period Crossover Trial in Chinese Healthy Subjects Under Fasting and Fed Conditions
Authors: Li Yan , Zhang Xueyuan , Qi Lu , Tong Yuanxu , Bai Haihong , Liu Ju , Liu Ying , Chen Youli , Wang Xinghe
Published: May 2022

The bioequivalence of the reference and test linagliptin formulations was assessed in healthy Chinese subjects under fasting and fed conditions. The study was designed as a single‐dose, randomized, open‐label, 2‐period crossover study with a 35‐day washout period between 2 administrations. Forty‐eight healthy subjects received 5 mg of test and reference linagliptin formulation orally under fasting condition. The geometric mean of the maximum observed linagliptin concentration (Cmax) for the test formulation was 4.9 ng/mL (reference, 5.0 ng/mL), the area under the plasma concentration–time curve from 0 to 72 hours (AUC0‐72) was 154.7 ng · h/mL (reference, 157.4 ng · h/mL). Thirty‐six subjects received 5 mg of test and reference linagliptin formulation orally under fed conditions. The geometric mean of Cmax for the test linagliptin formulation was 2.8 ng/mL (reference, 2.8 ng/mL), AUC0‐72 was 133.5 ng · h/mL (reference, 136.6 ng · h/mL). The 90%CIs for the test/reference ratio for Cmax and AUC0‐72 met the bioequivalence criteria (80%‐125%). The test and reference formulations of linagliptin were well tolerated and bioequivalent under fasting and fed conditions.
Execution trace‐based model verification to analyze multicore and real‐time systems
Authors: Beamonte Raphael , Ezzati‐Jivan Naser , Dagenais Michel R.
Published: May 2022

As a key part of model‐driven development, modeling allows users to represent the application workflow or to automatically generate source code. This is convenient for developers, particularly to create or improve real‐time applications embedded in complex systems. Multicore systems are difficult to debug because the concurrently running processes can interfere with each other. In real‐time systems, timing constraints add to the complexity, invalidating results when a deadline is missed. Tracing is usually the most accurate and reliable tool to study the runtime behaviour of those applications. However, the interpretation of voluminous detailed execution traces requires a deep understanding of the operating system and application behaviour, and time to dig through the millions of trace events.In this paper, we present the use of model‐based constraints on top of user‐space and kernel traces to provide weighted analysis results. Our algorithms have been applied to multiple traces showing common problems for multi‐core real‐time systems. The experimental results show that our algorithms can quickly identify many different types of problems with a low runtime, even for traces with millions of events, thus helping to save time when analyzing thousands of trace events for complex systems.
Dealloying Synthesis of Silicon Nanotubes for High‐Performance Lithium Ion Batteries
Authors: Zhao Jinfu , Wei Wenxian , Xu Na , Wang Xiaotong , Chang Limin , Wang Li , Fang Luan , Le Zaiyuan , Nie Ping
Published: May 2022

The front cover artwork is provided by Dr. Ping Nie and Prof. Limin Chang at Jilin Normal University. The image shows one‐dimensional silicon–nitrogen‐doped carbon nanotube composite fabricated through a dealloying process. The nanotube engineered silicon coupled with conductive carbon coating synergistically boosts the electrochemical performance. Read the full text of the Research Article at 10.1002/cphc.202100832.
Characterization Studies of Solution Grown Triglycine Oxalate Single Crystals
Authors: P. Justina Angelin , M. Daniel Sweetlin , P. Sumithraj Premkumar
Published: May 2022

Triglycine oxalate single crystal is grown by a slow evaporation technique from the saturated solution at the predetermined temperature. X‐ray diffraction studies of the grown crystal reveal that the grown crystal belongs to a monoclinic structure. The presence of elements and various functional groups of the triglycine oxalate is found in the Fourier transform infrared analysis. Optical transparency of the grown crystals is found to have the maximum transparency in the entire visible region. Thermogravimetric analysis shows that the grown crystals have three stages of decomposition. The microhardness of the grown crystals exhibits that the crystal is a soft material. The electrical studies such as dielectric constant, and dielectric loss are determined for the frequency range from 100 Hz to 200 kHz at different temperatures.
Culture and sustainable development: The role of merger and acquisition in Italian B Corps
Authors: Gazzola Patrizia , Amelio Stefano , Grechi Daniele , Alleruzzo Chiara
Published: May 2022

The aim of this study is to describe and analyse the relationship between the phenomenon of B Corp and M&A operations carried out by these companies. Italy is the second country at the international level and the first country at the European level to have been particularly active in this direction (Law n.208/2015). Therefore, a questionnaire was developed and sent to the certified Italian B Corps. The medium‐long‐term vision emerged in particular, and the values that guide these companies are ethics, sustainability and transparency. These are aspects that particularly characterise the ideals, identity and culture of B Corps, which are also involved in social and environmental issues. The research shows how corporate culture influences these companies from a merger and acquisition perspective. Cultural compatibility is important, as it allows the companies to operate according to common or similar visions regarding certain aspects that other companies probably find less important.
Preface to Special Issue on Biocatalysis as Key to Sustainable Industrial Chemistry
Authors: Alcántara Andrés R. , Domínguez de María Pablo , Littlechild Jennifer A. , Schürmann Martin , Sheldon Roger A. , Wohlgemuth Roland
Published: May 2022

In their Editorial for the Special Issue on Biocatalysis as Key to Sustainable Industrial Chemistry, Guest Editors Andrés Alcántara, Pablo Domínguez de María, Jennifer Littlechild, and Roland Wohlgemuth and their co‐workers on the European Society of Applied Biocatalysis’ (ESAB) Working Group on Sustainable Chemistry Martin Schürmann and Roger Sheldon discuss the Special Issue and the importance of biocatalysis in carrying out cutting‐edge industrial chemistry in a sustainable way, as well as the future prospects for the field.
A 12‐bit SC3 partially segmented current steering DAC with improved SFDR and bandwidth
Authors: Kumar Abhishek , Gupta Santosh Kumar , Bhadauria Vijaya
Published: May 2022

A 12‐bit self cascode capacitor compensated (SC3) partial segmented current steering digital to analog converter (DAC) is proposed and implemented in standard 180‐nm CMOS technology. The effect of the output capacitance at a higher frequency of operation is analyzed. Based on the analysis, a self cascode transistor is connected on the top of the differential switch with an “always‐on” biasing without compromising the voltage headroom. Besides, a compensation capacitor is also used at the output to improve spur free dynamic range (SFDR), which is obtained as 108 dB when sampled at 800 MS/s. The proposed architecture also offers high output impedance by more than 10 times compared with the cascode device. The proposed design also enhances the bandwidth of the circuit and is obtained to be 4 GHz with a power supply rejection ratio (PSRR) of 43 dB. It also has a total harmonic distortion (THD) of <3% up to input power of −4 dB and is also insensitive to process variations with a sensitivity of <0.5%.
Forward single‐cell sequencing into clinical application: Understanding of ageing and rejuvenation from clinical observation to single‐cell solution
Authors: Yan Furong , Li Zhangping , Powell Charles A. , Wang Xiangdong
Published: May 2022

Ageing is the part of natural biology lifespan and living pathology healthspan that is associated with impact from stress, environmental changes and diseases. The present Editorial emphasises the understanding of ageing biology and potential impact of rejuvenating interventions as a critical focus of clinical and translational medicine. The discovery and development of ageing‐associated biomarkers and therapeutic targets require understanding of the complexity of molecular metabolisms, immune responses and genetic regulations associated with ageing and rejuvenation. Transcriptomic patterns of circulating immune cells, red blood cells and platelets at single‐cell solution can be an important window to molecular mechanisms of ageing initiation and development. As part of programmes, deep understanding of ageing and rejuvenation correlations of clinical with single‐cell transcriptomics will provide more innovative opportunities to translate single‐cell RNA sequencing (scRNA‐seq) to clinical application.
Targeting DCLK1 overcomes 5‐fluorouracil resistance in colorectal cancer through inhibiting CCAR1/β‐catenin pathway‐mediated cancer stemness
Authors: Wang Lanqing , Zhao Lei , Lin Zhenyu , Yu Dandan , Jin Min , Zhou Pengfei , Ren Jinghua , Cheng Jing , Yang Kunyu , Wu Gang , Zhang Tao , Zhang Dejun
Published: May 2022

Background

To date, 5‐fluorouracil‐based chemotherapy is very important for locally advanced or metastatic colorectal cancer (CRC). However, chemotherapy resistance results in tumor recurrence and metastasis, which is a major obstacle for treatment of CRC.

Methods

In the current research, we establish 5‐fluorouracil resistant cell lines and explore the potential targets associated with 5‐fluorouracil resistance in CRC. Moreover, we perform clinical specimen research, in vitro and in vivo experiments and molecular mechanism research, to reveal the biological effects and the mechanism of DCLK1 promoting 5‐fluorouracil resistance, and to clarify the potential clinical value of DCLK1 as a target of 5‐fluorouracil resistance in CRC.

Results

We discover that doublecortin‐like kinase 1 (DCLK1), a cancer stem cell maker, is correlated with 5‐fluorouracil resistance, and functionally promotes cancer stemness and 5‐fluorouracil resistance in CRC. Mechanistically, we elucidate that DCLK1 interacts with cell cycle and apoptosis regulator 1 (CCAR1) through the C‐terminal domain, and phosphorylates CCAR1 at the Ser343 site, which is essential for CCAR1 stabilisation. Moreover, we find that DCLK1 positively regulates β‐catenin signalling via CCAR1, which is responsible for maintaining cancer stemness. Subsequently, we prove that blocking β‐catenin inhibits DCLK1‐mediated 5‐fluorouracil resistance in CRC cells. Importantly, we demonstrate that DCLK1 inhibitor could block CCAR1/β‐catenin pathway‐mediated cancer stemness and consequently suppresses 5‐fluorouracil resistant CRC cells in vitro and in vivo.

Conclusions

Collectively, our findings reveal that DCLK1 promotes 5‐fluorouracil resistance in CRC by CCAR1/β‐catenin pathway‐mediated cancer stemness, and suggest that targeting DCLK1 might be a promising method to eliminate cancer stem cells for overcoming 5‐fluorouracil resistance in CRC.
Single‐cell atlas of peripheral blood mononuclear cells from pregnant women
Authors: Chen Dongsheng , Wang Wei , Wu Linlin , Liang Langchao , Wang Shiyou , Cheng Yunfeng , Zhang Tongda , Chai Chaochao , Luo Qiuhong , Sun Chengcheng , Zhao Wandong , Lv Zhiyuan , Gao Ya , Wu Xiaoxia , Sun Ning , Zhang Yiwei , Zhang Jing , Chen Yixuan , Tong Jianing , Wang Xiangdong , Bai Yong , Sun Chaoyang , Jin Xin , Niu Jianmin
Published: May 2022

Background

During pregnancy, mother–child interactions trigger a variety of subtle changes in the maternal body, which may be reflected in the status of peripheral blood mononuclear cells (PBMCs). Although these cells are easy to access and monitor, a PBMC atlas for pregnant women has not yet been constructed.

Methods

We applied single‐cell RNA sequencing (scRNA‐seq) to profile 198,356 PBMCs derived from 136 pregnant women (gestation weeks 6 to 40) and a control cohort. We also used scRNA‐seq data to establish a transcriptomic clock and thereby predicted the gestational age of normal pregnancy.

Results

We identified reconfiguration of the peripheral immune cell phenotype during pregnancy, including interferon‐stimulated gene upregulation, activation of RNA splicing‐related pathways and immune activity of cell subpopulations. We also developed a cell‐type‐specific model to predict gestational age of normal pregnancy.

Conclusions

We constructed a single‐cell atlas of PBMCs in pregnant women spanning the entire gestation period, which should help improve our understanding of PBMC composition turnover in pregnant women.
Complex functional redundancy of Tbx2 and Tbx3 in mouse limb development
Authors: Lopatka Alika , Moon Anne M.
Published: May 2022

The limb phenotypes of Tbx2 and Tbx3 mutants are distinct: loss of Tbx2 results in isolated duplication of digit 4 in the hindlimb while loss of Tbx3 results in anterior polydactyly and posterior oligodactly in the forelimb. In the face of such disparate phenotypes, we sought to determine whether Tbx2 and Tbx3 have functional redundancy during development of the mouse limb. We found that sequential loss of alleles generates defects that are not simply additive of those observed in single mutants and that multiple structures in both the forelimb and hindlimb display compound sensitivity to decreased gene dosage.
Green roof irrigation management based on substrate water potential assures water saving without affecting plant physiological performance
Authors: Tomasella Martina , De Nardi Enrico , Petruzzellis Francesco , Andri Sergio , Castello Miris , Nardini Andrea
Published: May 2022

Irrigation management in extensive green roofs (EGRs) is crucial in Mediterranean and semi‐arid climates, as it should guarantee efficient water use while ensuring plant survival and vegetation cover. However, benefits of maintaining moderately low substrate water potential (Ψs) have not been adequately investigated to date. An irrigation control unit based on Ψs thresholds for irrigation (MediWater Safe [MWS]) was compared to a common irrigation timer maintaining Ψs ⁓ 0 MPa (CTR) in shrub‐vegetated Mediterranean EGR modules. The effect of the different irrigation regimes on substrate temperature, plant water relations (leaf conductance to water vapour, midday water potential and turgor loss point) and root vulnerability to heat stress via electrolyte leakage was tested in four shrub species. Decreasing Ψs thresholds to −0.4 MPa reduced irrigation volumes by 68% in 3 summer months. However, the MWS unit neither influenced plant water status and vegetation cover nor induced physiological acclimation responses. Brief irrigation cycles imposed by MWS in the warmest hours reduced substrate surface temperature by 3°C compared to CTR. Plant water status dynamics and root vulnerability to heat were species specific. Progressive stomatal closure and plant decline occurred only in Ceanothus thyrsiflorus and were associated to high root vulnerability to heat. Mortality occurred only in some Ceanothus plants in the CTR module, where higher Ψs favoured the expansion of Hyperucum x moserianum. The results suggest that selecting proper Ψs thresholds for irrigation could optimize EGR benefits, guaranteeing substantial water savings and proper plant establishment. Moreover, we claim root resistance to heat as a key parameter for plant selection in Mediterranean EGRs.
Facile One‐Pot Synthesis and Enhanced Photocatalytic Performances of Ternary Metal Sulfide Composite g‐C3N4/Cu3SnS4
Authors: Tian Yiming , Zhang Jiahua , Yang Xiao , Jia Dingxian
Published: May 2022

g‐C3N4/Cu3SnS4 (CN/CTS) nanocomposite photocatalysts were synthesized by solvothermal in‐situ reaction. SEM analyses show that petal‐like nanoparticles of Cu3SnS4 cover the nanosheets of g‐C3N4 in the CN/CTS composites. As the doping amount of CTS increases from 5 % to 20 %, the band gaps of the CN/CTS composites decrease from 2.66 eV to 2.46 eV. All CN/CTS composites display higher photocurrent densities than pristine g‐C3N4 and CTS, indicating high charge transfer capacity and low recombination of photogenerated electrons and holes for the CN/CTS composites under light irradiation. Photocatalytic experiments on the photodegradation of methylene blue (MB) showed that 59.3 %–82.7 % of MB were degraded in 3.5 h over the CN/CTS composites, which were higher than those of pristine g‐C3N4 and CTS due to the enhanced photocurrent densities of the CN/CTS composites. The catalytic performance of CN/CTS composites was affected by the doping amount of CTS. The CN/10 %‐CTS composite exhibited the best catalytic efficiencies with the MB degradation of 82.7 %, which is consistent with the result that it has the highest photocurrent density of 0.84 μA/cm2.
Dinuclear Diferrous Complexes of a Bis(tetradentate) Dinucleating Ligand: Influence of the Exogenous Ligands on the Molecular and Electronic Structures
Authors: Röhs Fridolin L. B. , Dammers Susanne , Stammler Anja , Oldengott Jan , Bögge Hartmut , Bill Eckhard , Glaser Thorsten
Published: May 2022

The ligand susan6−Me (susan6−Me=4,7‐dimethyl‐1,1,10,10‐tetra(6‐methyl‐2‐pyridylmethyl)‐1,4,7,10‐tetraazadecane) allows the synthesis of a peroxo complex that is only a transient species under catalytic conditions with the closely related ligand susan (susan=4,7‐dimethyl‐1,1,10,10‐tetra(2‐pyridylmethyl)‐1,4,7,10‐tetraazadecane). For the synthesis of a peroxo complex analogous to that of susan6−Me we present here the three air‐sensitive complexes [(susan){FeIICl2}2], [(susan){FeII(OTf)2}2], and [(susan){FeII(μ‐OH)2FeII}](ClO4)2 as potential precursors. [(susan){FeII(μ‐OH)2FeII}](ClO4)2 shows weak antiferromagnetic coupling and a g=16 EPR signal. Dissolving [(susan){FeII(OTf)2}2] in CH3CN forms [(susan){FeII(CH3CN)2}2]4+ that shows a spin transition upon cooling as evidenced by UV‐Vis, 1H NMR, and Mössbauer spectroscopies. In the UV‐Vis‐NIR spectra the combination of (i) the energy of the MLCT, (ii) the energy, and (iii) the splitting of the d–d transitions provide insight into the overall electron donation and into the different σ‐donor/π‐donor/π‐acceptor capabilities of the exogenous ligands. These experimental signatures provide insight into the molecular structures in solution e. g. during reactions with O2.
Enantioselective Synthesis of Spirocyclopentane Oxindoles Bearing Five Consecutive Stereocenters through Secondary Amine‐Catalyzed [3+2] Cycloaddition
Authors: Zhou Jing‐Wei , Chen Ben‐Hong , Zhang Feng‐Hua , Xue Jing , He Xiang‐Hong , Peng Cheng , Huang Wei , Zhao Qian
Published: May 2022

This work delineates a Michael‐initiated ring‐closing [3+2] cycloaddition of newly designed 3‐(1‐benzyl‐2‐oxoindolin‐3‐yl)pentane‐2,4‐diones with α,β‐unsaturated aldehydes. During the chiral secondary amine‐catalyzed cascade reaction, highly functionalized spirocyclopentane oxindole derivatives containing five consecutive stereogenic centers were formed, two of which were tetrasubstituted carbon. All the desired products are smoothly obtained in good yields (up to 90 %) with excellent enantioselectivities (up to >99 : 1 er) and diastereoselectivities (up to >95 : 5 dr). Meanwhile, the practicality of this strategy was highlighted by the further gram‐scale experiment and a set of synthetic transformations.
Crying does not alleviate acute pain perception: Evidence from an experimental study
Authors: Gračanin Asmir , Hendriks Michelle C. P. , Vingerhoets Ad J. J. M.
Published: May 2022

Background

Whereas previous studies revealed positive effects of emotional expressions such as swearing and laughing on acute pain, systematic research on the effects of crying on pain is missing. The rationale for the current study is that either a mere emotional distraction or changes in oxytocin and opioid levels represent a mechanism through which crying modulates pain, with the timing of mood changes as crucial information for distinguishing between potential mechanisms.

Methods

In two studies, we exposed participants (Study 1:n = 57; Study 2:n = 70) to a sad movie and measured their mood, and exposed them to pain induction procedures (electric shock and cold‐pressor test, respectively) before and after the film. Dependent variables were pain threshold, tolerance, and intensity. In addition to baseline and one immediate post‐crying mood and pain response measurement in both studies, in Study 2, we repeated these procedures 20 and 50 min later to discern between the potential role of neurobiological substances and distraction.

Results

Crying was elicited in 28 participants in Study 1 (49.1%) and 49 (70%) in Study 2. We found no systematic differences in pain and mood changes between criers and non‐criers and no systematic dose‐response relationship between crying and pain responses and mood. The only significant effects ran contrary to our hypotheses, showing detrimental effects of the occurrence (Study 1) and frequency of crying (both studies) on pain threshold.

Conclusions

Results do not support the idea that crying has pain‐alleviating effects, either via distraction or direct biological mechanisms.

Significance

Despite previous findings on pain alleviating effects of emotional expression and the widespread idea about the generally beneficial consequences of emotional crying, research on the possible pain alleviating effects of crying is largely missing. Two quasi‐experimental studies demonstrated that crying induced in laboratory conditions does not alleviate acute pain responses, suggesting that role of crying in pain interventions is doubtful. Less directly, results cast light on the role of emotional distraction from acute pain and possible crying‐related neurochemical changes.
Development and validation of capillary zone electrophoresis and high‐performance liquid chromatography methods for the determination of oral anticoagulant edoxaban in pharmaceutical tablets
Authors: Oliveira Rocha Manoelly , Bordignon Primieri Gabriele , Ribeiro Wingert Nathalie , Arguello Da Silva Jacqueline , Steppe Martin
Published: May 2022

The incidence of thrombotic complications in SARS‐CoV‐2 infections has become a global concern; thus, anticoagulants are an integral part of the treatment. Edoxaban (EDX) is an oral anticoagulant suitable for pharmacologic thromboprophylaxis. Herein, two novel analytical methods for EDX determination in tablets are developed and validated using capillary zone electrophoresis (CZE) and high‐performance liquid chromatography (HPLC). Operating conditions such as the electrolyte's concentration and pH value, injection time, volume, and the capillary temperature, were optimized. The methods were successfully validated by establishing the linearity, intra‐ and inter‐day precisions (relative standard deviation [%]), accuracy, and robustness. Adequate separation of excipients and degradation products of EDX generated by stress degradation conditions demonstrated the stability‐indicating capability of the methods. The analytical procedures were linear in the range of 25–125 µg/ml (r > 0.999), with the limits of detection and quantification of 3.26 and 10.87 µg/ml for CZE and 0.740 and 2.78 µg/ml for HPLC. Although both methodologies are suitable for determining EDX in tablets, CZE provides a greener alternative due to low‐cost analysis using less organic solvents and minimizing waste generation.