bluuebunny/crossref_metadata_2025_split huggingface dataset:
1,10‐Phenanthroline Copper(I) Complexes with A3 Coupling to Access Allenes for Cycloaddition Reactions
Authors: Kim Hyun Jo , Lee Ji Eun , Koyyada Ganesh , Lakavathu Mohan , Kim Jae Hong 
Published: March 2022

AbstractPropargylamines are significant building blocks for the generation of polyfunctional amino analogues, natural products, and pharmacologically active drugs. Herein we report the most straightforward approach is to use 1,10‐phenanthroline copper(I) complexes as a catalyst to promote the (Alkyne‐Alkyne‐Amine) A3 coupling reaction between cyclic secondary amines and two terminal alkynes that generates a ketimine intermediate in situ through hydroamination, which subsequently interacts with the alkenyl copper complex to produce tetrasubstituted propargylamine. In the addition of zinc halide, the propargylamines converted into trisubstituted allenes with up to 90% yield. When Sc(OTf)3 is used to perform the [4+2] cycloaddition reaction with enophile (alkene), the cyclized product obtained in up to 72% yield. On the other hand, the allene was subjected to a metal‐free intermolecular cyclization reaction to produce the highly substituted pyridine derivative, although this provides only up to 30% yield.
Hydrazone and Oxime Olefination via Ruthenium Alkylidenes
Authors: Nasrallah Daniel J. , Zehnder Troy E. , Ludwig Jacob R. , Steigerwald Daniel C. , Kiernicki John J. , Szymczak Nathaniel K. , Schindler Corinna S. 
Published: March 2022

AbstractWe describe the development of an efficient method for the olefination of hydrazones and oximes. The key design approach that enables this transformation is tuning of the energy/polarity of C=N π‐bonds by employing heteroatom functionalities (NR2, OR). The resulting hydrazones or oximes facilitate olefination with ruthenium alkylidenes. Through this approach, we show that air‐stable, commercially available ruthenium alkylidenes provide access to functionalized alkenes (20 examples) in ring‐closing reactions with yields up to 88 %.
Integrated Ring‐Chain Design of a New Fluorinated Ether Solvent for High‐Voltage Lithium‐Metal Batteries
Authors: Zhou Tianhong , Zhao Yan , El Kazzi Mario , Choi Jang Wook , Coskun Ali 
Published: March 2022

AbstractEther‐based electrolytes offer promising features such as high lithium‐ion solvation power and stable interface, yet their limited oxidation stability impedes application in high‐voltage Li‐metal batteries (LMBs). Whereas the fluorination of the ether backbone improves the oxidative stability, the resulting solvents lose their Li+‐solvation ability. Therefore, the rational molecular design of solvents is essential to combine high redox stability with good ionic conductivity. Here, we report the synthesis of a new high‐voltage fluorinated ether solvent through integrated ring‐chain molecular design, which can be used as a single solvent while retaining high‐voltage stability. The controlled Li+‐solvation environment even at low‐salt‐concentration (1 M or 2 M) enables a uniform and compact Li anode and an outstanding cycling stability in the Li|NCM811 full cell (20 μm Li foil, N/P ratio of 4). These results show the impact of molecular design of electrolytes towards the utilization of LMBs.
Generation and Release of OH Radicals from the Reaction of H2O with O2 over Soot
Authors: He Guangzhi , Ma Jinzhu , Chu Biwu , Hu Renzhi , Li Hao , Gao Meng , Liu Yuan , Wang Yonghong , Ma Qingxin , Xie Pinhua , Zhang Guoxian , Zeng Xiao Cheng , Francisco Joseph S. , He Hong 
Published: March 2022

AbstractOH radicals in the air maintain the oxidizing power of the troposphere. A conventional view is that particulate matter (PM) in the atmosphere is a major sink of OH radicals, thereby lowering the oxidizing power of atmosphere in the event of high‐level PM. By contrary, our joint experimental/theoretical study reveals a new mechanism for the generation of gaseous OH radicals by carbonaceous soot particles. We show that water and O2 react on carbonaceous surfaces and give rise to gaseous OH radicals under irradiation. With ample delocalized π electrons, carbonaceous surfaces enable the easy desorption of hydroxyl groups to produce gaseous OH radicals, evidenced by direct observation of the steady generation of OH radicals on a carbonaceous surface. Our results reveal a new chemical mechanism for the production of OH radicals.
Mediating Oxidation of Thioethers with Iodine—A Mild and Versatile Pathway to Trigger the Formation of Peptide Hydrogels
Authors: Nowak Benedikt P. , Schlichter Lisa , Ravoo Bart Jan 
Published: March 2022

AbstractThe development of redox‐triggerable peptide hydrogels poses fundamental challenges, since the highly specific peptide architectures required inevitably limit the versatility of such materials. A powerful, yet rarely applied approach to bypass those barriers is the application of a mediating redox reaction to gradually decrease the pH during hydrogel formation. We report a versatile strategy to trigger the formation of peptide hydrogels from readily accessible acid‐triggerable gelators by generating protons by oxidation of thioethers with triiodide. Adding thiodiglycol as a readily available thioether auxiliary to the basic precursor solution of a peptide gelator efficiently yielded hydrogels after mixing with triiodide, as studied in detail for Nap‐FF and demonstrated for other peptides. Furthermore, incorporation of the thioether moiety in the gelator backbone via the amino acid methionine, as shown for the tailormade Nap‐FMDM peptide, reduces the number of required additives.
The Iran nuclear deal: A Bionian commentary
Authors: Alisobhani Afsaneh Kiany 
Published: March 2022

AbstractThe threat of a nuclear war became more evident when President Trump walked away from the Joint Comprehensive Plan of Action—the Iran nuclear deal. The agreement, reached between Iran and the P5+1 (The United States, Britain, China, France, Russia, and Germany) in 2015, was the most important nonproliferation agreement in decades. In this paper, the author provides a detailed history of the relationship between Iran and the United States starting with the Central Intelligence Agency's covert Operation Ajax in 1953 that led to the overthrow of Dr. Mohammad Mossadegh, the democratically elected prime minister of Iran. The impact of the United States' role in the Iran–Iraq war as well as President Bush's declaration of Iran as a part of the “Axis of Evil” will be discussed in the context of the present situation. The challenges facing the Biden administration in negotiating with Iran will be explored, given the past and current chasm between Iran and the United States. The author draws on Wilfred Bion's model of the mind and offers a perspective on the unconscious group dynamics present in the current geopolitical climate around the threat of the impasse, or possible collapse of the negotiations, in reviving the nuclear deal between Iran and the United States. The paradoxes and dilemmas faced by both parties will be examined through the vertex of Bion's concept of the container/contained, and the significance of the “function of linking” as the foundation of psychic existence.
Ratiometric fluorimetric and colorimetric probe for sensing and imaging pH changes in living cells
Authors: Wei Zhiwen , Jia Juan , Gong Yige , Wang Yandan , Niu Weifen 
Published: March 2022

AbstractCell, enzyme, and tissue activity in living organisms are closely related to intracellular pH. Detecting the changes of intracellular pH is important to understanding the physiological and pathological changes in the process of crucial cell metabolism. A pH probe (HTBI) based on hemicyanine was synthesized. The probe solution displayed a marked colour change from yellow to amaranth with the pH increase from neutral to basic; simultaneously, the emission spectra showed a significant red shift. The probe exhibited a ratiometric fluorescence emission (F586nm/F542nm) characteristic of pKa8.82. As expected, HTBI exhibited high sensitivity and selectivity for pH, fine photostability, reversibility, and low cytotoxicity. Therefore, it would be a very useful tool for measuring the intracellular pH changes.
Application of a luminous intensity variation fluorescent probe for the detection of ferric ions
Authors: Duan Ning , Guo Feng , Deng Bing , Yang Shaoxiang , Tian Hongyu , Sun Baoguo 
Published: March 2022

AbstractA luminous intensity variation fluorescent probe (Probe 1) for the detection of ferric ion was developed. The quantitative range of Fe3+ content detected was 0–600 μM with the limit of detection at 0.76 μM. Furthermore, after 20 min of Fe3+ addition, the intensity of the luminescence of Probe 1 solution gradually decreased with increase in Fe3+ concentration. In addition, the B and G values of these images showed a linear relationship with Fe3+ concentration (0–500 μM). Probe 1 was successfully used for the rapid determination of Fe3+ concentration in real samples. This study demonstrates that Probe 1 is an excellent tool for the rapid determination of Fe3+ content in real samples using a smart phone without professional equipment.
Predictor variables of mental health in the Spanish population confined by COVID‐19
Authors: Robles‐Bello María Auxiliadora , Sánchez‐Teruel David , Valencia Naranjo Nieves , Sohaib Lorabi 
Published: March 2022

AbstractBackgroundDrastic changes in the lifestyle of individuals have been caused by coronarivus SARS‐CoV‐2 with lethal effects associated with COVID‐19, which acts as a stressor for the population with adverse effects on mental health status. The aim was to identify which sociodemographic variables and psychological factors predict psychological disorders in the general Spanish population.MethodsThe sample consisted of 699 people exposed to a confinement situation, where 402 (57.51%) were women and 297 (42.49%) were men, between 18 and 73 years old (M = 27.79; SD = 12.68). Different sociodemographic and psychological variables were assessed to see if they predicted levels of anxiety and depression.ResultsThe results identify the predictive capacity of some sociodemographic risk variables such as sex (β = .144; IC95% = 1.341–3.376) and living with people who are ill with COVID‐19 (β = .088; IC95% = 1.157–6.785), as well as protective factors such as self‐efficacy (β = −.126; IC95% = −0.282–0.066) and hope (β = −.429; IC95% = −0.591–0.408) in mental health. In predicting anxiety levels, self‐efficacy and hope are protective factors, especially when living with people in essential services. In levels of depression, only hope is considered a protective factor in people living with patients infected by COVID‐19.ConclusionsThis study is the first to advance in the understanding of sociodemographic and psychological variables in a Spanish sample subjected to the stressful and traumatic effects of the SARS‐CoV‐2 viral agent.
Evaluation of correlation between CD44, radiotherapy response, and survival rate in patients with advanced stage of head and neck squamous cell carcinoma (HNSCC)
Authors: Dubey Parul , Gupta Rajeev , Mishra Anupam , Kumar Vijay , Bhadauria Smrati , Bhatt Madan Lal Brahma 
Published: March 2022

AbstractPurposeCancer stem cells (CSCs) constitute a distinctive subpopulation of cancer cells that are competent in tumor initiation, invasion, recurrence, and resistance to chemoradiotherapy. CD44, a hyaluronic acid (HA) receptor has been considered as a potential CSC marker in head and neck cancer. The purpose of this study is to evaluate the correlation between CD44 and clinicopathological parameters, treatment response, survival, and recurrence.MethodsThe CD44 expression was examined by immunohistochemistry (IHC) in 90 samples of head and neck squamous cell carcinoma (HNSCC) confirmed patients. The expression of CD44 and its association with clinicopathological parameters, treatment response, and survival was determined.ResultsIn all HNSCC patient samples, CD44 was expressed consistently at different intensities. Tumor size (p < 0.001), stage (p < 0.001), and treatment response (p < 0.001) showed statistically significant association with CD44 expression. Alcohol and CD44 were observed as independent predictors of response to radiotherapy using multivariate ordinal logistic regression analysis. Analysis of 2‐year overall survival (OS) showed that CD44 expression (p = 0.02), tumor size (p = 0.001), lymph node status (p < 0.001), stage (p < 0.001), and grade (p = 0.007) were significantly associated with OS. Using Cox regression analysis, lymph node status (p = 0.001), grade (p < 0.001), recurrence (p < 0.001), and CD44 expression (p = 0.003) were found to be potential independent predictors of OS.ConclusionOur findings suggest that CD44 contributes to resistance to radiotherapy and poor OS. The results also suggest that except for CD44 there could be other factors such as lymph node metastasis, grade, and alcohol which should be investigated as potential targets for therapy.
Improved risk scoring systems for colorectal cancer screening in Shanghai, China
Authors: Wu Wei‐Miao , Gu Kai , Yang Yi‐Hui , Bao Ping‐Ping , Gong Yang‐Ming , Shi Yan , Xu Wang‐Hong , Fu Chen 
Published: March 2022

AbstractBackgroundAn optimal risk‐scoring system enables more targeted offers for colonoscopy in colorectal cancer (CRC) screening. This analysis aims to develop and validate scoring systems using parametric and non‐parametric methods for average‐risk populations.MethodsScreening data of 807,695 subjects and 2806 detected cases in the first‐round CRC screening program in Shanghai were used to develop risk‐predictive models and scoring systems using logistic‐regression (LR) and artificial‐neural‐network (ANN) methods. Performance of established scoring systems was evaluated using area under the receiver operating characteristic curve (AUC), calibration, sensitivity, specificity, number of high‐risk individuals and potential detection rates of CRC.ResultsAge, sex, CRC in first‐degree relatives, chronic diarrhoea, mucus or bloody stool, history of any cancer and faecal‐immunochemical‐test (FIT) results were identified as predictors for the presence of CRC. The AUC of LR‐based system was 0.642 when using risk factors only in derivation set, and increased to 0.774 by further incorporating one‐sample FIT results, and to 0.808 by including two‐sample FIT results, while those for ANN‐based systems were 0.639, 0.763 and 0.805, respectively. Better calibrations were observed for the LR‐based systems than the ANN‐based ones. Compared with the currently used initial tests, parallel use of FIT with LR‐based systems resulted in improved specificities, less demands for colonoscopy and higher detection rates of CRC, while parallel use of FIT with ANN‐based systems had higher sensitivities; incorporating FIT in the scoring systems further increased specificities, decreased colonoscopy demands and improved detection rates of CRC.ConclusionsOur results indicate the potentials of LR‐based scoring systems incorporating one‐ or two‐sample FIT results for CRC mass screening. External validation is warranted for scaling‐up implementation in the Chinese population.
Female case with misdiagnosis of hemophilia A who underwent total knee arthroplasty: A case report
Authors: Bari Alireza , Mansouritorghabeh Hassan 
Published: March 2022

AbstractA female was diagnosed with hemophilia A. She had undergone bilateral total knee arthroplasty. She had a history of numerous hemorrhages including hemarthrosis. After further investigations, the diagnosis of von Willebrand disease type 2N was confirmed. The differential diagnoses for hemophilia A include von Willebrand disease, rare bleeding disorders, and severe platelet disorders.
Ru on N‐doped Carbon for the Selective Hydrogenolysis of Sugars and Sugar Alcohols
Authors: Beine Anna Katharina , Ludovicy Jil , Chai Jiachun , Hofmann Jan P. , Glotzbach Christoph , Hausoul Peter J. C. , Palkovits Regina 
Published: March 2022

AbstractGlycols are accessible via metal‐catalyzed hydrogenolysis of sugar alcohols such as xylitol obtained from hemicellulose. Ru‐based catalysts are highly active but also catalyze side‐reactions such as decarbonylation and deoxygenation. To achieve high selectivity, these reactions need to be suppressed. In our study, we introduce heteroatom doped carbon materials as catalyst supports providing high selectivity. Heteroatom doping with nitrogen and oxygen was achieved by treating activated carbon with HNO3, NH3 and H2 or carbonization of organic precursors. For all N‐doped materials a high glycol selectivity of
80 % for sorbitol and xylitol and 44 % for xylose and glucose was reached. XPS analysis confirms the presence of different nitrogen species at the carbon surface and varying ligand effects for oxygen and nitrogen. Oxygen has an electron withdrawing effect on ruthenium and leads to a decreased activity. Nitrogen has weaker electron withdrawing properties, resulting in an enhanced selectivity.
An Intermetallic CaFe6Ge6 Approach to Unprecedented Ca−Fe−O Electrocatalyst for Efficient Alkaline Oxygen Evolution Reaction
Authors: Yang Hongyuan , Hausmann J. Niklas , Hlukhyy Viktor , Braun Thomas , Laun Konstantin , Zebger Ingo , Driess Matthias , Menezes Prashanth W. 
Published: March 2022

AbstractBased on the low‐cost and relatively high catalytic activity, considerable efforts have been devoted towards developing redox‐active transition metal (TM)‐oxygen electrocatalysts for the alkaline oxygen evolution reaction (OER) while the role of redox‐inactive alkaline earth metals has often been neglected in OER. Herein, for the first time, we developed a novel ternary intermetallic CaFe6Ge6 precatalyst, whose surface rapidly transforms into a porous ultrathin Ca−Fe−O heteroshell structure during alkaline OER through the oxidative leaching of surficial Ge. Benefiting from synergistic effects, this highly efficient OER‐active material with distinct Ca−Fe−O layers has a large electrochemical surface area and more exposed active Fe sites than a Ca‐free FeOx phase. Also, the presence of Ca in Ca−Fe−O is responsible for the enhanced transport and activation of hydroxyls and related OER reaction intermediate as unequivocally illustrated by a combination of quasi in‐situ Raman spectroscopy and various ex‐situ methods.
Participation and losses in multi‐level marketing: Evidence from a Federal Trade Commission settlement
Authors: Bäckman Claes , Hanspal Tobin 
Published: March 2022

AbstractMore than 20 million Americans are affiliated with multi‐level marketing firms (MLMs), but there is little empirical evidence on who participates in this controversial part of today's labor market. We link data on 350,000 individuals cited in an Federal Trade Commission settlement with one of the largest MLMs to detailed county‐level information. We find that the share of refund claimants is greater in areas with higher median income and where women are absent from the labor market, suggesting value in flexible work. However, check amount, a proxy for losses, are correlated with higher inequality and lower social capital, suggesting that the pitfalls accrue to vulnerable groups.
Structures and Reactivities of Cocrystals Involving Diboronic Acids and Bipyridines: In Situ Linker Reaction and 1D‐to‐2D Dimensionality Change via Crystal‐to‐Crystal Photodimerization
Authors: Guadalupe Vasquez‐Ríos  María , Campillo‐Alvarado Gonzalo , Swenson Dale C. , Höpfl Herbert , MacGillivray Leonard R. 
Published: March 2022

AbstractCocrystallizations of diboronic acids [1,3‐benzenediboronic acid (1,3‐bdba), 1,4‐benzenediboronic acid (1,4‐bdba) and 4,4’‐biphenyldiboronic acid (4,4’‐bphdba)] and bipyridines [1,2‐bis(4‐pyridyl)ethylene (bpe) and 1,2‐bis(4‐pyridyl)ethane (bpeta)] generated the hydrogen‐bonded 1 : 2 cocrystals [(1,4‐bdba)(bpe)2] (1), [(1,4‐bdba)(bpeta)2] (2), [(1,3‐bdba)(bpe)2(H2O)2] (3) and [(1,3‐bdba)(bpeta)2(H2O)] (4), wherein 1,3‐bdba involved hydrated assemblies. The linear extended 4,4’‐bphdba exhibited the formation of 1 : 1 cocrystals [(4,4'‐bphdba)(bpe)] (5) and [(4,4'‐bphdba‐me)(bpeta)] (6). For 6, a hemiester was generated by an in‐situ linker transformation. Single‐crystal X‐ray diffraction revealed all structures to be sustained by B(O)−H⋅⋅⋅N, B(O)−H⋅⋅⋅O, Ow−H⋅⋅⋅O, Ow−H⋅⋅⋅N, C−H⋅⋅⋅O, C−H⋅⋅⋅N, π⋅⋅⋅π, and C−H⋅⋅⋅π interactions. The cocrystals comprise 1D, 2D, and 3D hydrogen‐bonded frameworks with components that display reactivities upon cocrystal formation and within the solids. In 1 and 3, the C=C bonds of the bpe molecules undergo a [2+2] photodimerization. UV radiation of each compound resulted in quantitative conversion of bpe into cyclobutane tpcb. The reactivity involving 1 occurred via 1D‐to‐2D single‐crystal‐to‐single‐crystal (SCSC) transformation. Our work supports the feasibility of the diboronic acids as formidable structural and reactivity building blocks for cocrystal construction.
Performance analysis of disease diagnostic system using IoMT and real‐time data analytics
Authors: Yıldırım Emre , Çalhan Ali , Cicioğlu Murtaza 
Published: March 2022

AbstractIn this article, the Internet of Medical Things (IoMT) framework based on Apache Spark big data processing technology is proposed for real‐time analysis of health data obtained from wireless body area networks (WBANs), which is one of the most important components of IoMT. The proposed framework consists of four layers: data source, data collection, data analytics and visualization. In addition, the proposed IoMT framework is presented with two different disease prediction scenarios, diabetes and heart disease. Diabetes and heart disease prediction processes are carried out using the random forest (RF), logistic regression (LR) and support vector machine (SVM) algorithms belonging to the Apache Spark machine learning library (MLlib). The analysis of health data generated in WBANs takes place in real‐time in the Apache Spark‐based data analytics layer. In this study, the performances of MLlib algorithms in the real‐time model developed for heart and diabetes disease are examined. The SVM algorithm with an accuracy rate of 93.33% for heart disease and the LR algorithm with an accuracy rate of 78.89% for diabetes are found to provide the best performances.
Integrating Bimetal Alloy into N‐Doped Carbon Nanotubes@Nanowires Superstructure for Zn‐Air Batteries
Authors: Xu Chen , Niu Yanli , Gong Shuaiqi , Liu Xuan , Xu Mingze , Liu Tao , Chen Zuofeng 
Published: March 2022

AbstractExploring bifunctional oxygen electrocatalysts with low cost and high performance is critical to the development of rechargeable zinc‐air batteries, but it still remains a huge challenge. In this work, a “coordination construction‐pyrolysis/self‐catalyzed growth” approach was employed to fabricate branches@trunks‐like, N‐doped carbon nanotubes@nanowires superstructure with uniformly incorporated CoFe alloy nanoparticles (CoFe@CNTs‐NWs). The rational design of such hierarchical architecture could effectively enlarge the exposure of active sites, modulate their electronic structure, and assist the electron transfer and mass diffusion, thus benefiting both ORR and OER. The resultant CoFe@CNTs‐NWs displayed prominent bifunctional electrocatalytic activity and stability with a minimized oxygen overpotential of 0.71 V. When used as a cathode for zinc‐air batteries, it provided a high peak power density of 131 mW cm−2 and remarkable charge‐discharge stability for at least 400 cycles (130 h). This study presents a successful demonstration for optimizing the electrocatalytic performance by elaborate nanostructure and carbon matrix hybridization with simultaneous modulation of electronic structure, thus providing a new avenue to the rational design of transition metal‐based oxygen electrocatalysts.