bluuebunny/crossref_metadata_2025 huggingface dataset:
Oxidative Addition von C−F‐Bindungen an das Silanid‐Anion [Si(C2F5)3]−
Authors: Tiessen Natalia , Keßler Mira , Neumann Beate , Stammler Hans‐Georg , Hoge Berthold
Published: February 2022

Verbindungen von Hauptgruppenelementen in niedrigen Oxidationsstufen sind in der Lage, die Reaktivität von Übergangsmetallkomplexen nachzuahmen. Wie Letztere neigen niedervalente Hauptgruppenelementverbindungen zur Änderung ihrer Oxidationsstufe und Koordinationszahl um +2, wodurch sie die wesentlichen Voraussetzungen für oxidative Additionen erfüllen. Prominente Beispiele für Hauptgruppenelementverbindungen, die mit Organohalogeniden R−X (R=Alkyl, Aryl, X=F, Cl, Br, I) oxidative Additionen eingehen, sind Carbene und ihre höheren Analoga. Kürzlich wurde auch über Aluminyl‐Anionen berichtet, die wie Carbene und Silylene starke σ‐Bindungen von R−X‐Spezies oxidativ addieren können. Hier stellen wir nun mit dem Tris(pentafluorethyl)silanid‐Anion, [Si(C2F5)3]−, das erste Anion aus der 14. Gruppe vor, welches C−F‐Bindungen im Sinne einer oxidativen Addition zu spalten vermag. Dies ermöglichte die Isolierung von nicht‐chelatierten Tetraorganofluorosilicat‐Salzen, die unseres Wissens bisher nur als reaktive Zwischenstufen nachgewiesen wurden.
Drastische Ereignisse und langsame Transformation definieren die Struktur eines aktiven Kupfer‐Zink‐Aluminiumoxid‐Katalysators für die Methanol Synthese
Authors: Beck Arik , Newton Mark A. , Zabilskiy Maxim , Rzepka Przemyslaw , Willinger Marc G. , van Bokhoven Jeroen A.
Published: February 2022

Der Kupfer‐Zink‐Aluminiumoxid‐Katalysator (CZA) ist einer der wichtigsten industriellen Katalysatoren. Jedoch versteht man die komplexe CZA‐Struktur nur teilweise und das bremst seine Weiterentwicklung. Um einen sehr aktiven und stabilen Katalysator zu erzeugen sind optimale Aktivierungsbedingungen in Wasserstoff essentiell. In dieser Arbeit folgen wir mithilfe von operando Röntgenadsorptionspektroskopie und ‐diffraktion der Entwicklung eines industriellen CZA‐Katalysatorvorläufer zum arbeitenden Katalysator. Zwei Ereignisse während der Aktivierung führen zu drastischen Veränderung in den kupfer‐ und zinkhaltigen Komponenten des CZA‐Katalysators und bestimmen die Struktur des fertigen Katalysators: Erstens, die Reduktion des ursprünglichen Kupfer(II)oxids und, zweitens, das Kristallwachstum und Reoxidierung von Zinkoxid während des Wechsels zu katalytischen Bedingungen. Diese drastischen Ereignisse werden von anderen graduellen Transformationen begleitet. Um maßgeschneiderte Aktivierungsprotokolle, die die maximale Lebensdauer und Aktivität des Katalysators erzielen, zu entwickeln, müssen wir diesen Transformationen verstehen.
Access to a Labile Monomeric Magnesium Radical by Ball‐Milling
Authors: Jędrzkiewicz Dawid , Mai Jonathan , Langer Jens , Mathe Zachary , Patel Neha , DeBeer Serena , Harder Sjoerd
Published: February 2022

In order to isolate a monometallic Mg radical, the precursor (Am)MgI⋅(CAAC) (1) was prepared (Am=tBuC(N‐DIPP)2, DIPP=2,6‐diisopropylphenyl, CAAC=cyclic (alkyl)(amino)carbene). Reduction of a solution of 1 in toluene with the reducing agent K/KI led to formation of a deep purple complex that rapidly decomposed. Ball‐milling of 1 with K/KI gave the low‐valent MgI complex (Am)Mg⋅(CAAC) (2) which after rapid extraction with pentane and crystallization was isolated in 15 % yield. Although a benzene solution of 2 decomposes rapidly to give Mg(Am)2 (3) and unidentified products, the radical is stable in the solid state. Its crystal structure shows planar trigonal coordination at Mg. The extremely short Mg−C distance of 2.056(2) Å indicates strong Mg−CAAC bonding. Calculations and EPR measurements show that most of the spin density is in a π* orbital located at the C−N bond in CAAC, leading to significant C−N bond elongation. This is supported by calculated NPA charges in 2: Mg +1.73, CAAC −0.82. Similar metal‐to‐CAAC charge transfer was calculated for M0(CAAC)2 and [MI(CAAC)2+] (M=Be, Mg, Ca) complexes in which the metal charges range from +1.50 to +1.70. Although the spin density of the radical is mainly located at the CAAC ligand, complex 2 reacts as a low‐valent MgI complex: reaction with a I2 solution in toluene gave (Am)MgI⋅(CAAC) (1) as the major product.
A Highly Fluorescent Dinuclear Aluminium Complex with Near‐Unity Quantum Yield**
Authors: Portwich Flavio L. , Carstensen Yves , Dasgupta Anindita , Kupfer Stephan , Wyrwa Ralf , Görls Helmar , Eggeling Christian , Dietzek Benjamin , Gräfe Stefanie , Wächtler Maria , Kretschmer Robert
Published: February 2022

The high natural abundance of aluminium makes the respective fluorophores attractive for various optical applications, but photoluminescence quantum yields above 0.7 have yet not been reported for solutions of aluminium complexes. In this contribution, a dinuclear aluminium(III) complex featuring enhanced photoluminescence properties is described. Its facile one‐pot synthesis originates from a readily available precursor and trimethyl aluminium. In solution, the complex exhibits an unprecedented photoluminescence quantum yield near unity (Φabsolute 1.0±0.1) and an excited‐state lifetime of 2.3 ns. In the solid state, J‐aggregation and aggregation‐caused quenching are noted, but still quantum yields of 0.6 are observed. Embedding the complex in electrospun non‐woven fabrics yields a highly fluorescent fleece possessing a quantum yield of 0.9±0.04.
In Situ Hydrogen Evolution Monitoring During the Electrochemical Formation and Cycling of Pressed‐Plate Carbonyl Iron Electrodes in Alkaline Electrolyte
Authors: Weinrich Henning , Pleie Jan , Schmid Bernhard , Tempel Hermann , Kungl Hans , Eichel Rüdiger‐A.
Published: February 2022

The hydrogen evolution reaction (HER) on iron is a parasitic side reaction for the reduction of iron (hydr)oxide in alkaline electrolyte, which lowers the Coulombic efficiency of iron‐based batteries. Tackling this issue, here we investigate the HER on iron electrodes by in situ gas chromatography, allowing for a quantitative correlation of the applied electrode potential and the resulting hydrogen evolution. As a result, it is shown that the HER follows a distinctive profile corresponding to the electrode potential and changes depending on the state of the iron electrode formation. Moreover, it is shown that the charging efficiency of the iron electrode can be increased by an alteration of the charging procedure, i. e., a more negative cut‐off potential for the discharge and a potential limitation for the recharge. In this study, a charging efficiency of 96.7 % is achieved, using an optimized charging procedure for a formed carbonyl iron electrode containing 8.5 wt.% of Bi2S3.
Nucleic acids movement and its relation to genome dynamics of repetitive DNA
Authors: Kejnovsky Eduard , Jedlicka Pavel
Published: February 2022

There is growing evidence of evolutionary genome plasticity. The evolution of repetitive DNA elements, the major components of most eukaryotic genomes, involves the amplification of various classes of mobile genetic elements, the expansion of satellite DNA, the transfer of fragments or entire organellar genomes and may have connections with viruses. In addition to various repetitive DNA elements, a plethora of large and small RNAs migrate within and between cells during individual development as well as during evolution and contribute to changes of genome structure and function. Such migration of DNA and RNA molecules often results in horizontal gene transfer, thus shaping the whole genomic network of interconnected species. Here, we propose that a high evolutionary dynamism of repetitive genome components is often related to the migration/movement of DNA or RNA molecules. We speculate that the cytoplasm is probably an ideal compartment for such evolutionary experiments.
Involvement of the BDNF–TrkB–KCC2 pathway in neuropathic pain after brachial plexus avulsion
Authors: Zhao Shuo , Wang Fengyu , Wang Li , Xu Yali , Lv Li , Duan Wenxu , Bai Runze , Meng Zhao , Shao Xinzhong
Published: February 2022

Introduction

Brachial plexus avulsion significantly increased brain‐derived neurotrophic factor (BDNF) release in the spinal cord. Here we investigated the involvement of the BDNF–TrkB–KCC2 pathway in neuropathic pain caused by BPA injury. We hypothesized that activation of BDNF–TrkB may inhibit neuronal excitability by downregulating KCC2 to maintain a high intracellular Cl‐concentration. We established a neuropathic pain rat model by avulsion of the lower trunk brachial plexus, and investigated the effects of the TrkB‐specific antibody K‐252a on the expression of BDNF, TrkB, and KCC2.

Methods

We randomly divided 40 male SD rats into four groups. In the brachial plexus avulsion group, C8‐T1 roots were avulsed from the spinal cord at the lower trunk level. In the K252a group, 5uL K252a was applied intrathecally daily for three days after avulsion. In the sham surgery group, expose only and without damage. The control group did not undergo any treatment. Mechanical hyperalgesia and cold allodynia were analyzed by electronic pain measuring instrument and acetone spray method at different time points on days 1, 3, 7, 10, 14, and 21 after surgery. At 21 days after surgery, the expression of BDNF and TrkB in dorsal horn neurons and GFAP in astrocytes were detected by immunohistochemistry at the C5‐T1 segment of the spinal cord. The expression levels of BDNF, TrkB, and KCC2 in the C5‐T1 spinal cord were measured by Western Blot at 7 and 21 days.

Results

Mechanical hyperalgesia and cold allodynia were significantly reduced in the K252a group compared with the brachial plexus avulsion group. Compared with the BPA group, BDNF, TrkB and GFAP were significantly decreased in the K252a group at 21 days after treatment by immunohistochemical test. In the WB test, the expressions of BDNF and TrkB in the K252a group were quantitatively detected to be decreased, while the expression of KCC2 was increased, which was obvious at 7 and 21 days.

Conclusion

BDNF‐TrkB‐KCC2 pathway can significantly relieve neuropathic pain after BPA, and is a potential target for the treatment of neuropathic pain.
Dissemination of validated health literacy videos: A tailored approach
Authors: Blee Shannon M. , Facdol Jamil , Dixon Margie D. , Master Viraj , Switchenko Jeffrey M. , Pentz Rebecca D.
Published: February 2022

Background

Previously, we showed that chemotherapy terminology is difficult for patients to understand. Therefore, we developed short videos explaining key terminology and though proven effective, they will only be helpful if appropriately disseminated. Therefore, we aimed to determine the best dissemination method at three different healthcare settings.

Methods

With consent, we interviewed healthcare workers from (1) an academic cancer center, Winship Cancer Institute (Winship) serving higher SES patients, (2) an inner‐city, safety‐net hospital Grady Memorial (GMH), (3) clinics serving rural Georgia, from the Winship Community Network (Network). All interviews were transcribed and analyzed using a semantic content analysis method. Suggested dissemination plans were then implemented.

Results

Twenty‐two Winship, 11 GMH, and 4 Network healthcare workers were interviewed. Seventy‐two percent (n = 8) of the GMH and 100% (n = 4) of Network healthcare workers felt that the best place for patients to view the videos was in the clinic, compared to 27% (n = 6) of the Winship clinicians. 68% (n = 15) of the Winship clinicians stated an app would be the most useful format, compared to 27% (n = 3) at GMH, and 0% at Network sites. Video viewing increased after dissemination plans were implemented.

CONCLUSION

Educational materials explaining oncology treatment terminology enhance patient understanding, yet without proper dissemination, these tools may never reach the intended patient population. Our study shows that dissemination plans need to be tailored to each individual patient population, with rural and lower SES patients needing to view the videos during clinic visits, and patients of more means viewing them using technology at home.
Primary mucoepidermoid carcinoma of the intrahepatic bile duct: A case report
Authors: Kato Kenichi , Hara Yasuyuki , Nishida Akiko , Suzuki Shuhei , Sato Hidenori , Chin Masahiro , Hashizume Eiji
Published: February 2022

Mucoepidermoid carcinoma (MEC) is the most common salivary gland carcinoma; however, hepatobiliary MEC is extremely rare. A 74‐year‐old patient was diagnosed with hepatobiliary MEC after hepatectomy. We considered its origin could be the peribiliary glands. Its genome profile was similar to salivary MEC rather than standard biliary tract carcinoma.
MELAS with multiple stroke‐like episodes due to the variant m.13513G>A in MT‐ND5
Authors: Ghosh Ritwik , Dubey Souvik , Bhuin Subhas , Lahiri Durjoy , Ray Biman Kanti , Finsterer Josef
Published: February 2022

Mitochondrial encephalopathy, lactic acidosis, and stroke‐like episodes (MELAS) is characterized by metabolic stroke, seizures, cognitive decline, lactic acidosis, ragged‐red fibers, headache, and vomiting, and in 80% of cases due to the mtDNA variant m.3243A>G. We report the case of a MELAS patient carrying a variant in subunit‐5 of the respiratory chain (MT‐ND5), rarely reported in MELAS. The patient is a 33‐year‐old male, who experienced a series of stroke‐like episodes (StLEs) since age 23 years, which manifested clinically as seizures transient sensory disturbances, weakness, and visual or cognitive impairment. Over 9 years, these StLEs were misinterpreted as ischemic strokes, respectively, as cerebral vasculitis. He presented with mild, recurrent elevations of the creatine kinase. Initially, anti‐seizure drugs and steroids appeared to be beneficial. Despite good recovery of each single StLE, the patient experienced a progressive decline of cognitive functions and activities of daily living. Cerebral imaging showed corresponding stroke‐like lesions in changing locations. At age 32y, genetic work‐up revealed the variant m.13513G>A in MT‐ND5. The patient profited significantly from a cocktail with anti‐oxidants/cofactors. This case shows that the variant m.13513G>A in MT‐ND5 can manifest as MELAS that StLEs recover spontaneously and that the course of MELAS is slowly progressive.
A Study on the Binary and Ternary CuZnAl Catalysts without Additives for Efficient CO Hydrogenation to Ethanol
Authors: Liu Jing , Fan Jinchuan , Li Fang , Gong Jie , Wang Sen , Yang Denghui , Huang Wei
Published: February 2022

Synthesis of ethanol from syngas on CuZnAl catalyst without additives has attracted substantial interest. However, the active sites and the reaction mechanism are still not fully understood due to the complexity of the ternary system. Herein, a series of binary (CuZn, CuAl, ZnAl) and ternary CuZnAl catalysts were prepared using complete liquid method for CO hydrogenation to ethanol. The results show that CAT‐CZ and CAT‐ZA possess much higher ability for ethanol synthesis than CAT‐CA, which is attributed to the presence of the key species Zn and the strong interaction at the interface. In situ DRIFTS measurements reveal the intermediate species of each catalyst, indicating that there are different carbon chain growth paths in CAT‐CZ and CAT‐ZA. The desirable catalytic CO hydrogenation performance (10.87 % of CO conversion and 57.18 % proportion of ethanol in total alcohol) on CAT‐CZA can be attributed the existence of multiple mechanisms for the ethanol production process.
Tuning the C/N Ratio of C‐Rich Graphitic Carbon Nitride (g‐C3N4) Materials by the Melamine/Carboxylic Acid Adduct Route
Authors: Gashi Arianit , Parmentier Julien , Fioux Philippe , Marsalek Roman
Published: February 2022

C‐rich graphitic carbonitride materials (CNx) with a large range of compositions have been prepared thanks to the self‐assembly, in different ratios, of melamine (M) and a panel of polycarboxylic acids (A) such as oxalic, tartaric and citric acid. The thermal conversion of the formed adducts (MAy), led to CNx phases, with x ranging from 0.66 to 1.4 (x=1.33 for g‐C3N4 for comparison). The properties of these materials were examined by different techniques (XRD, Raman spectroscopy, TEM, TGA, XPS and DRIFT). It appears that the increase in the C content is associated with the disappearance of the long‐range order of heptazine units and an increase in the sub‐nanometer carbon‐rich cluster size within the graphitic g‐C3N4 structure. This trend is followed by a significant increase in the interlayer spacing and a lower proportion of N=C−N bonds compared to C=C bonds. The thermal stability under an inert atmosphere of these phases and their UV‐Visible absorbance properties were also investigated.
Parasitic Light Absorption, Rate Laws and Heterojunctions in the Photocatalytic Oxidation of Arsenic(III) Using Composite TiO2/Fe2O3
Authors: Bullen Jay C. , Heiba Hany F. , Kafizas Andreas , Weiss Dominik J.
Published: February 2022

Composite photocatalyst‐adsorbents such as TiO2/Fe2O3 are promising materials for the one‐step treatment of arsenite contaminated water. However, no previous study has investigated how coupling TiO2 with Fe2O3 influences the photocatalytic oxidation of arsenic(III). Herein, we develop new hybrid experiment/modelling approaches to study light absorption, charge carrier behaviour and changes in the rate law of the TiO2/Fe2O3 system, using UV‐Vis spectroscopy, transient absorption spectroscopy (TAS), and kinetic analysis. Whilst coupling TiO2 with Fe2O3 improves total arsenic removal by adsorption, oxidation rates significantly decrease (up to a factor of 60), primarily due to the parasitic absorption of light by Fe2O3 (88 % of photons at 368 nm) and secondly due to changes in the rate law from disguised zero‐order kinetics to first‐order kinetics. Charge transfer across this TiO2‐Fe2O3 heterojunction is not observed. Our study demonstrates the first application of a multi‐adsorbate surface complexation model (SCM) towards describing As(III) oxidation kinetics which, unlike Langmuir‐Hinshelwood kinetics, includes the competitive adsorption of As(V). We further highlight the importance of parasitic light absorption and catalyst fouling when designing heterogeneous photocatalysts for As(III) remediation.
Für ein strahlendes Lächeln
Authors: Emden Markus , Hild Pitt , Murer Livia
Published: February 2022

Anliegen der in loser Folge erscheinenden Versuche ist es, Impulse für chemische Versuche zu geben, die gefahrlos zu Hause mit haushaltsüblichen Gegenständen durchgeführt werden können. Sie können damit als Quelle für das gemeinsame Ausprobieren mit Kindern zuhause dienen, in Kindergärten oder an Schulen sowie zur Verwendung bei Tagen der offenen Tür. Ein Stückweit sind sie zu verstehen als Antwort auf den oft gehörten Satz: „Ach, Du bist Chemiker/in!? Dann mach doch mal eben ein Experiment.“
Beamforming design with fully connected analog beamformer using deep learning
Authors: P. Jeyakumar , M. Tharanitaran N. , E. Malar , P. Muthuchidambaranathan
Published: February 2022

Beamforming (BF) architecture, an emerging approach for large‐scale antenna arrays, is a key task for the next decade's communication systems. The proposed approach in millimeter wave transmission is a fully connected analog phase‐shifter‐based BF architecture with limited radio frequency chains and imperfect channel state information (CSI). Deep learning (DL) is a powerful method for channel estimation and signal identification in wireless communications. Hence, this research proposes a DL‐enabled beamforming neural network (BFNN) which can be programmed to optimize the beamformer to attain better spectral efficiency. Simulation findings reveal that the proposed BFNN achieves significant performance gain and high robustness to imperfect CSI. The proposed BFNN greatly decreases the computational complexity by 0.16 million floating point operations (FLOPs) over 0.26 million FLOPs by conventional BF algorithms.
An adult case of congenital duodenal diaphragm that was successfully treated by endoscopic resection using a grasping‐type scissor forceps
Authors: Fukuda Shin‐ichiro , Ichida Kaoru , Kitagawa Yusuke , Nakano Kayoko , Tomohito Chaen , Yoshimura Daisuke , Ochiai Toshiaki , Ihara Eikichi , Ogawa Yoshihiro
Published: February 2022

Congenital duodenal diaphragm (CDD) is a rare disease that is usually diagnosed in the neonatal period; however, it is sometimes diagnosed later in the adult period. A 39‐year‐old woman was referred to our hospital due to tarry stool and anemia. Emergent esophagogastroduodenoscopy (EGD) revealed an obstructing membranous structure with a small orifice in the second portion of the duodenum, together with dilatation of the bulbar part. The membranous structure was accompanied by a Dieulafoy‐like vessel on the backside, which was considered to have caused tarry stool and anemia. The Dieulafoy‐like vessel was successfully treated by endoscopic hemostasis. Based on the computed tomographic gastrography and barium duodenography findings, it was diagnosed as CDD. Later, endoscopic resection of the diaphragm was conducted by an endoscopic submucosal dissection (ESD)‐based procedure, with the use of an electrosurgical grasping‐type scissor forceps (ClutchCutter [CC]). There were no procedure‐related complications. The definite diagnosis of CDD was made based on the observation of typical structures in a pathological examination. This is the first case report of adult CDD that was successfully treated by endoscopic resection using ESD‐based techniques with a CC.
The long and the short of it: Mechanisms of synchronous and compensatory dynamics across temporal scales
Authors: Shoemaker Lauren G. , Hallett Lauren M. , Zhao Lei , Reuman Daniel C. , Wang Shaopeng , Cottingham Kathryn L. , Hobbs Richard J. , Castorani Max C. N. , Downing Amy L. , Dudney Joan C. , Fey Samuel B. , Gherardi Laureano A. , Lany Nina , Portales‐Reyes Cristina , Rypel Andrew L. , Sheppard Lawrence W. , Walter Jonathan A. , Suding Katharine N.
Published: February 2022

Synchronous dynamics (fluctuations that occur in unison) are universal phenomena with widespread implications for ecological stability. Synchronous dynamics can amplify the destabilizing effect of environmental variability on ecosystem functions such as productivity, whereas the inverse, compensatory dynamics, can stabilize function. Here we combine simulation and empirical analyses to elucidate mechanisms that underlie patterns of synchronous versus compensatory dynamics. In both simulated and empirical communities, we show that synchronous and compensatory dynamics are not mutually exclusive but instead can vary by timescale. Our simulations identify multiple mechanisms that can generate timescale‐specific patterns, including different environmental drivers, diverse life histories, dispersal, and non‐stationary dynamics. We find that traditional metrics for quantifying synchronous dynamics are often biased toward long‐term drivers and may miss the importance of short‐term drivers. Our findings indicate key mechanisms to consider when assessing synchronous versus compensatory dynamics and our approach provides a pathway for disentangling these dynamics in natural systems.
KIAA1199 drives immune suppression to promote colorectal cancer liver metastasis by modulating neutrophil infiltration
Authors: Wang Haihong , Zhang Biying , Li Ruiqi , Chen Jiayuan , Xu Guojie , Zhu Ying , Li Jiao , Liang Qing , Hua Qingling , Wang Lanqing , Wen Lu , Jin Min , Fan Jun , Zhang Dejun , Zhao Lei , Yu Dandan , Lin Zhenyu , Ren Jinghua , Zhang Tao
Published: February 2022

Background and Aims

Metastasis is the primary cause of cancer mortality, and colorectal cancer (CRC) frequently metastasizes to the liver. Our previous studies demonstrated the critical role of KIAA1199 in tumor invasion and metastasis in CRC. In the present study, we described an immune regulatory effect of KIAA1199 that creates a permissive environment for metastasis.

Approach and Results

Flow cytometry was used to examine the effects of KIAA1199 on the infiltration of tumor immune cells. Neutrophils and T cells were isolated, stimulated, and/or cultured for in vitro function assays. In the patients with CRC, high expression levels of KIAA1199 were associated with an increased neutrophil infiltration into the liver. This result was further validated in mouse metastasis models. The increased influx of neutrophils contributed to the KIAA1199‐driven CRC liver metastasis. Mechanistically, KIAA1199 activated the TGFβ signaling pathway by interacting with the TGFBR1/2 to stimulate CXCL1 and CXCL3 production, thereby driving the aggregation of immunosuppressive neutrophils. Genetic blockade or pharmacologic inhibition of KIAA1199 restored tumor immune infiltration, impeded tumor progression, and potentiated response to immune checkpoint blockade (ICB).

Conclusions

These findings indicated that KIAA1199 could facilitate the liver infiltration of immunosuppressive neutrophils via the TGFβ–chemokine (C‐X‐C motif) ligand (CXCL)3/1–CXCR2 axis, which might be clinically targeted for the treatment of hepatic metastasis.
Usability Analysis of an MBSE Model of Standard Operating Procedures
Authors: Bashatah Jomana , Sherry Lance
Published: February 2022

Standard Operating Procedures (SOPs) are the “glue” that holds the operator‐plant system together throughout the missions performed by the system. For this reason, developing and modeling the SOPs early in the development life cycle, can inform the design, and reduce development and operational costs accrued due to sub‐ optimal operator‐plant interaction. This paper describes how to apply the popular Heuristic Evaluation method for usability analysis on SOPs modeled using Action Diagrams in a Model‐based System Engineering (MBSE) development environment.
The pieces of the smallholder puzzle: The add‐in role of farmers' characteristics in irrigation improvement projects in the old lands of Egypt
Authors: Salman Maher , Fertő Imre , Pék Éva , El‐Desouky Ibrahim Abd Al‐Latif , Zaki Saad , Darwesh Reda , Lebdi Fethi , Alali Qotada
Published: February 2022

Irrigation development is essential for reducing vulnerability to water resource scarcity, food insecurity, and climate change impacts in Egypt. The centralized irrigation development must, however, overcome the challenges of the diversity of smallholders and the pre‐existing, individualistic irrigation management. The purpose of this paper is to examine the farmers' characteristics that influence the design and success of irrigation improvement programmes in the Old Lands of Egypt. The paper investigates this issue from the perspectives of farmers by analysing farm features, agricultural practices, irrigation practices, and satisfaction with water services. The clustering method is applied to create farmer groups within the geographical area of the programme and seek consistent differences that affect the outcome of irrigation improvement. The results show that farmers are less diverse in their agrotechnology and more heterogenous in terms of capacities, livelihood sources, and land tenure structures. The article argues that grouping methods to deploy improved irrigation infrastructure should give more consideration to the farmers' individual features. Programmes intended to replicate such irrigation development or leverage the existing results should address these particularities to create a socially adaptive environment for future irrigation investment in Egypt.
Engineer a pre‐metastatic niched microenvironment to attract breast cancer cells by utilizing a 3D printed polycaprolactone/nano‐hydroxyapatite osteogenic scaffold – An in vitro model system for proof of concept
Authors: Xiong Qisheng , Zhang Ningze , Zhang Miaomiao , Wang Meng , Wang Lizhen , Fan Yubo , Lin Chia‐Ying
Published: February 2022

Breast cancer bone metastasis is not a random process. It is affected by the local microenvironment which determines the propensity of cancer cells to invade and colonize into the secondary sites. This microenvironment is termed a pre‐metastatic niche. With the flexibility to incorporate different biofactors, tissue‐engineering scaffolds provide an advantageous environment to promote “designed” osteogenesis that may mimic the bony pre‐metastatic niche. In the current study, designed polycaprolactone (PCL) scaffolds enriched with nano‐hydroxyapatite (nHA) were fabricated through three‐dimensional (3D) printing. Subsequently, human mesenchymal stem cells (hMSCs) were seeded onto PCL‐nHA scaffolds for osteogenic differentiation to establish the pre‐metastatic niched microenvironment. Furthermore, transwell migration assay was used to investigate recruitment of MDA‐MB‐231, MCF‐7, and MDA‐MB‐453 breast cancer cells to the osseous PCL‐nHA scaffolds. Our results showed that the mRNA levels of alkaline phosphatase (ALP), runt‐related transcription factor 2 (Runx2), and osteocalcin (OCN) of hMSCs on the PCL‐nHA scaffolds were dramatically increased compared those with the PCL scaffolds (control) at day 7, 14, and 28. Meanwhile, the migration analysis showed that the higher maturation of osteogenesis and bone metabolism collectively contributed to the creation of a more favorable niched site for the cancerous invasion. Moreover, one of the hypothesized key mediators for the promoted migration, CXCL12, was confirmed using an assay of antagonist LIT‐927. This early study demonstrated that a designed tissue engineering scaffold can be utilized to create a bone‐mimicking environment that serves as a novel platform to recapitulate the pre‐metastatic niche and help interrogate the scheme of bone metastasis by breast cancer.
Structural, biocompatibility, and antibacterial properties of Ge–DLC nanocomposite for biomedical applications
Authors: Arslan Mehmet Enes , Kurt Mustafa Şükrü , Aslan Naim , Kadi Abdurrahim , Öner Sena , Çobanoğlu Şeymanur , Yazici Ayşenur
Published: February 2022

Integrative production of new nanocomposites has been used to enhance favorable features of biomaterials for unlocking ultimate potential of different molecules. In the present study, advantageous properties of diamond like carbons (DLC) and germanium (Ge) like greater biocompatibility and antibacterial attributes were aimed to combined into a thin film. For this purpose, 400 nm DLC–Ge nanocomposite was coated on the borosilicate glasses via the magnetron sputtering and surface characteristics was analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and The Raman spectrum. Biocompatibility analysis were performed by 3‐(4,5‐Dimethylthiazol‐2‐yl) (MTT) cell viability assay and Hoechst 33258 fluorescent staining genotoxicity assessments on the human fibroblast cell line (HDFa). Finally, antibacterial properties of DLC–Ge nanocomposite coatings were investigated by Pseudomonas aeruginosa (ATCC 27853) and Staphylococcus aureus (ATCC 25923) bacterial attachment analysis. As a result of magnetron sputtering coating, nearly 400 nm thick DLC–Ge nanocomposite film showed a smooth, a non‐porous, and a dense characteristic. Cell viability analysis showed that Ge–DLC coatings permits %95 cell surface growth of fibroblast cells. Also, there were no significant difference in aspect of nuclear abnormalities compared to the (−) control which showed nonmutagenic features of the thin film. Finally, antibacterial attachment analysis put forth that Ge–DLC coatings inhibits bacterial adhesion as %40 and %25 rates for P. aeruginosa and S. aureus bacterial strains, respectively. From these results, DLC–Ge nanocomposites could be proposed as a potential new biomaterial for various biomedical applications.
UK clinical and community psychology: Exploring personal and professional connections
Authors: Thompson Miles , Stuart Jenny , Vincent Rose E. , Goodbody Louise
Published: February 2022

This paper explores the personal and professional connections between clinical psychologists in the United Kingdom (UK) and critical/community psychology (CCP). Specifically, it asks how clinical psychologists define the area, how they relate to it and how they apply it in their work. Twenty clinical psychologists responded to an online survey, 12 of whom went on to take part in a follow‐up telephone interview. Data were analysed using inductive thematic analysis. The results are divided into three sections: i. “describing CCP”: social justice and a questioning stance are considered, ii. “relating to CCP”: an interplay between lifespan events and personal responses are described and iii. “applying CCP”: a dynamic between role‐specific applications and reality checks that either enable or constrain is illustrated. Although the continued need for a CCP is described, the results highlight both challenges and tensions of practising CCP within clinical psychology.
Academic performance and attitudes of dental students impacted by COVID‐19
Authors: Hayes Christina , Mears Michael , Rowan Sean , Dong Fanglong , Andrews Elizabeth
Published: February 2022

Objectives

Previous studies only focused on attitudes and behaviors of US dental students without examining direct effects of the COVID‐19 pandemic on academic performance. This study examined effects of COVID‐19 pandemic on dental students’ academic performance, self‐reported attitudes, behavior, and service utilization. We hypothesized that the pandemic provided more beneficial learning environments.

Methods

This mixed study design implemented a cross sectional survey with retrospective extraction of students’ academic grades. A survey of 274 predoctoral students assessed self‐reported attitudes/behaviors and service utilization. First year Doctor of Dental Medicine (DMD1) 2021–2024 students’ academic performance data were extracted. Independent t‐test and chi‐square crosstab analyses were conducted assessing differences between pre‐COVID and post‐COVID cohorts.

Results

Participants’ academic grades identified statistically significant associations between pre‐/post‐COVID grades in five of 12 DMD1 courses. Grade percentages identified increased average grades in four of 12 DMD1 courses, with one of 12 courses demonstrating decreased grade percentage. Half of survey participants were female (n = 37/72, 51.4%), 79.2% were 25–34 years old, and 44.4% (n = 32) were DMD 2024. About 1/5 (20.8%, n = 15) sought counseling/therapy. Students agreed staying home allowed more time to study (66.7%, n = 48), while 59.2% (n = 42) reported increased financial concerns. A majority reported lacking in‐person group studying decreased performance, and 55.6% (n = 40) reported feeling depressed.

Conclusion

Students performed better overall in courses delivered remotely with clinical application and team‐based engagement. Students performed equally overall; however, the majority had concerns regarding finances, group studying, and mental health challenges. This highlights the need for more readily available resources at institutions.
K‐29 linked ubiquitination of Arrdc4 regulates its function in extracellular vesicle biogenesis
Authors: Farooq Ammara Usman , Gembus Kelly , Sandow Jarrod J. , Webb Andrew , Mathivanan Suresh , Manning Jantina A. , Shah Sonia S. , Foot Natalie J. , Kumar Sharad
Published: February 2022

Extracellular vesicles (EVs) are important mediators of intercellular communication. However, EV biogenesis remains poorly understood. We previously defined a role for Arrdc4 (Arrestin domain containing protein 4), an adaptor for Nedd4 family ubiquitin ligases, in the biogenesis of EVs. Here we report that ubiquitination of Arrdc4 is critical for its role in EV secretion. We identified five potential ubiquitinated lysine residues in Arrdc4 using mass spectrometry. By analysing Arrdc4 lysine mutants we discovered that lysine 270 (K270) is critical for Arrdc4 function in EV biogenesis. Arrdc4K270R mutation caused a decrease in the number of EVs released by cells compared to Arrdc4WT, and a reduction in trafficking of divalent metal transporter (DMT1) into EVs. Furthermore, we also observed a decrease in DMT1 activity and an increase in its intracellular degradation in the presence of Arrdc4K270R. K270 was found to be ubiquitinated with K‐29 polyubiquitin chains by the ubiquitin ligase Nedd4‐2. Thus, our results uncover a novel role of K‐29 polyubiquitin chains in Arrdc4‐mediated EV biogenesis and protein trafficking.
The impact of child migration on the health and well‐being of parents left behind
Authors: Bridges Sarah , Liu Lefan
Published: February 2022

This paper uses data from the China Health and Retirement Survey to estimate the causal effect child out‐migration has on the health of parents in China. For rural parents, we show that after controlling for self‐selection, child out‐migration has a detrimental effect not only on subjective well‐being and mental health but also on cognitive function and physical health when measured using a series of clinical tests and health biomarkers. In contrast, for urban parents, only a few health effects are significant, and those that are tend to be positive. In terms of the mechanism through which migration affects parental health, we find that it is differences in the level of physical support that parents require that is central to explaining many of the health effects we observe. For those who require little physical support, the income effect helps to mitigate the negative effects associated with child out‐migration, while for more vulnerable groups of parents, the economic benefits of migration are currently no substitute for the loss of informal support networks when a child migrates.
Synthesis of carbon‐14 and stable isotope labeled Censavudine
Authors: Burrell Richard C. , Bonacorsi Samuel J. , Ortiz Adrian , Benkovics Tamas , Shi Zhongping
Published: February 2022

Censavudine is a nucleoside reverse transcriptase inhibitor (NRTI) explored clinically by Bristol Myers Squibb for the treatment of human immunodeficiency virus‐1 (HIV‐1). As part of the development process, a carbon‐14 labeled analog was synthesized for use in a human absorption, distribution, metabolism, and excretion (ADME) study. A stable isotope labeled analog was also synthesized for use as a mass spectrum internal standard in bioanalytical assays to accurately quantify the concentration of the drug in biological samples. Carbon‐14 labeled Censavudine was synthesized in 10 steps in a 9% overall yield from carbon‐14 labeled trimethylsilylacetylene. A total of 4.44 mCi of material was prepared with a specific activity of 0.25 μCi/mg. The radiochemical and UV purities were 99% and it met all of the specifications for use in a human clinical study. Deuterium labeled Censavudine was synthesized in two steps in a 68% overall yield from [D4]‐thymine. A total of 237 mg were prepared with a UV purity of 99%.
Historical droughts in Irish catchments 1767–2016
Authors: O'Connor Paul , Murphy Conor , Matthews Tom , Wilby Robert L.
Published: February 2022

Recent prolonged dry periods in summer 2018 and spring 2020 have reawakened interest in drought in Ireland, prompting questions regarding historical drought occurrence and potential long‐term risks. Employing 250 years of monthly precipitation and flow reconstructions, we investigate historical drought in Irish catchments evaluating the characteristics (number of events, duration, and deficits) of moderate, severe, and extreme droughts as well as the propagation of meteorological to hydrological drought. Using standardized indices, we identify three distinct catchment types. Cluster 1 catchments, located in the wetter northwest are characterized by small areas, low groundwater storage, and the highest frequency of hydrological drought relative to other catchments. Cluster 3 catchments, located in the drier east and southeast have larger areas, greater groundwater storage, the highest frequency of meteorological drought but the least hydrological droughts. However, once established, droughts in Cluster 3 tend to be more persistent with large accumulated deficits. Cluster 2 catchments, located in the southwest and west, are intermediate to Clusters 1 and 3, with hydrological droughts typically of shorter durations, reduced accumulated deficits but greater mean deficits. The most extreme droughts based on accumulated deficits across all catchments occurred in 1803–1806, 1854–1859, 1933–1935, 1944–1945, 1953–1954, and 1975–1977. Although not as severe, droughts in 1887–1888, 1891–1894, and 1971–1974 also appear as significant extremes. Changes in drought characteristics reveal a complex picture with the direction, magnitude, and significance of trends dependent on the accumulation period used to define drought, the period of record analysed, and the reference period used to standardize indices. Of particular note is a tendency towards shorter, more intense meteorological and hydrological droughts. Our findings offer important insight for drought and water management in Ireland given the paucity of extreme droughts in short observed river flow records.
Preparation, tribological behaviour and lubrication performances of nano‐CaWO4:Eu3+ as EP additive in water‐soluble fluid for laminated copper cladding steel sheet during cold rolling
Authors: Xiong Sang , Wu Hao , Liang Dong
Published: February 2022

CaWO4: Eu3+ nanoparticles in acidity (pH = 5) and alkalinity (pH = 10) solutions were prepared by citric acid method, and characterised by SEM and XRD. Tribological behaviour and lubrication performances of nano‐CaWO4:Eu3+ as extreme pressure (EP) additives in water‐soluble fluid for laminated copper cladding steel sheet during cold rolling were studied. These results suggest that CaWO4:Eu3+ exhibits excellent extreme pressure property, antiwear and antifriction performances in water‐soluble fluid, especially when the optimal concentration was 0.3 wt%. The value of WSD reduced from 0.62 to 0.40 mm and the value of COF decreased from 0.078 to 0.068, the surface quality of rolled sheet is improved with the addition of nano‐CaWO4:Eu3+ (pH = 5 and pH = 10), because the tribofilm (~20 nm) composed of Fe2O3, WO3, Eu2O and CaO was formed on the worn surface to avoid direct contact between metal friction pairs in sliding process.
Forcing axioms for λ‐complete μ+$\mu ^+$‐c.c.
Authors: Shelah Saharon
Published: February 2022

We consider forcing axioms for suitable families of μ‐complete ‐c.c. forcing notions. We show that some form of the condition “ have a in ” is necessary. We also show some versions are really stronger than others.
Report of rare and novel mutations in candidate genes in a cohort of hearing‐impaired patients
Authors: Liu Min , Liang Yue , Huang Bixue , Sun Jincangjian , Chen Kaitian
Published: February 2022

Background

Many hearing‐impaired patients carry mutations in rare or novel genes undetected in regular genetic hot regions/genes screening.

Methods

We collected clinical and genetic data from subjects with hearing loss who visited our department for genetic counseling. Next‐generation sequencing was conducted after 154 deafness‐related genes were captured using a designed genes panels in 14 unrelated families (37 participants). The results were filtered and assessed with in silico tools, in combination with pedigree mapping.

Results

Ten mutations in regular deafness genes (GJB2, SLC26A4) and uncommon genes (OTOF, MYO7A, MYO15A, and KARS) were detected, which constituted 57.2% of yielded rate. In particular, two patients with nonsyndromic deafness carried biallelic KARS mutations. In addition, we identified an unreported digenic mutational inheritance in GRP98/USH2A genes in a proband with isolated hearing loss. Functional analyses and molecular modeling suggested the damaging consequence of these variants on encoded proteins. According to the variant pathogenicity guidelines, the 17 identified variants in total were classified as “pathogenic” or “likely pathogenic.”

Conclusion

The candidate mutations in deafness genes were suggested to be co‐segregated in at least 57.2% of the studied pedigrees. This is the new report of rare/novel mutations causing inherited hearing loss in Chinese.
Numerical solutions of nonhomogeneous Rosenau type equations by quintic B‐spline collocation method
Authors: Özer Sibel , Yağmurlu Nuri Murat
Published: February 2022

In this study, a numerical scheme based on a collocation finite element method using quintic B‐spline functions for getting approximate solutions of nonhomogeneous Rosenau type equations prescribed by initial and boundary conditions is proposed. The numerical scheme is tested on four model problems with known exact solutions. To show how accurate results the proposed scheme produces, the error norms defined by L2 and L∞ are calculated. Additionally, the stability analysis of the scheme is done by means of the von Neuman method.
Metal‐free Kinugasa reaction catalyzed by external electric field
Authors: Mandal Sucharita , Datta Ayan
Published: February 2022

Oriented external electric field (OEEF) is in recent interest for its ability to promote reactivity and selectivity in chemical transformations. This article reports facile metal‐free [3 + 2] cycloaddition for the Kinugasa reaction in the presence of OEEF. The free energy of activation is reduced by 4.9 kcal/mol due to a parallel electric field in the orthogonal direction to the reaction axis, Fy = 5.0 V Å−1. As a proof‐of‐principle of this model, a multidrug‐resistant (MDR) antibiotic, carbapenem could be envisioned from the [3 + 2] cycloaddition of a cyclic nitrone and an acetonide substituted acetylene. This reaction shows an interesting ambiaxial electric field‐induced catalysis with a reduced reaction barrier for anti‐parallel fields, −Fx (reaction axis) and −Fz and parallel field along +Fy. This is due to the out‐of‐plane bending of the acetonide unit containing two highly electronegative oxygen atoms. As a result, off‐axial tensorial responses to the electric‐fields on the barriers are observed. Such ambiaxial OEEF driven catalysis is interesting because it expands the utility of electric fields for large enzymes. Disorder and dynamical effects of side chains are envisioned to cause non‐null responses to applied field for parallel or anti‐parallel directions along axes.
Role of cardiopulmonary exercise test in the prediction of hemodynamic impairment in patients with pulmonary arterial hypertension
Authors: Pezzuto B. , Badagliacca R. , Muratori M. , Farina S. , Bussotti M. , Correale M. , Bonomi A. , Vignati C. , Sciomer S. , Papa S. , Palazzo Adriano E. , Agostoni P.
Published: February 2022

Periodic repetition of right heart catheterization (RHC) in pulmonary arterial hypertension (PAH) can be challenging. We evaluated the correlation between RHC and cardiopulmonary exercise test (CPET) aiming at CPET use as a potential noninvasive tool for hemodynamic burden evaluation. One hundred and forty‐four retrospective PAH patients who had performed CPET and RHC within 2 months were enrolled. The following analyses were performed: (a) CPET parameters in hemodynamic variables tertiles; (b) position of hemodynamic parameters in the peak end‐tidal carbon dioxide pressure (PETCO2) versus ventilation/carbon dioxide output (VE/VCO2) slope scatterplot, which is a specific hallmark of exercise respiratory abnormalities in PAH; (c) association between CPET and a hemodynamic burden score developed including mean pulmonary arterial pressure (mPAP), pulmonary vascular resistance (PVR), cardiac index, and right atrial pressure. VE/VCO2 slope and peak PETCO2 significantly varied in mPAP and PVR tertiles, while peak oxygen uptake (peak VO2) and O2 pulse varied in the tertiles of all hemodynamic parameters. PETCO2 versus VE/VCO2 slope showed a strong hyperbolic relationship (R2 = 0.7627). Patients with peak PETCO2 > median (26 mmHg) and VE/VCO2 slope < median (44) presented lower mPAP and PVR (p < 0.005) than patients with peak PETCO2 < median and VE/VCO2 slope > median. Multivariate analysis individuated peak VO2 (p = 0.0158) and peak PETCO2 (p = 0.0089) as hemodynamic score independent predictors; the formula 11.584 − 0.0925 × peak VO2 − 0.0811 × peak PETCO2 best predicts the hemodynamic score value from CPET data. A significant correlation was found between estimated and calculated scores (p < 0.0001), with a precise match for patients with mild‐to‐moderate hemodynamic burden (76% of cases). The results of the present study suggest that CPET could allow to estimate the hemodynamic burden in PAH patients.