bluuebunny/crossref_metadata_2025_split huggingface dataset:
Oxygen Evolution Reaction on 2D Ferromagnetic Fe3GeTe2: Boosting the Reactivity by the Self‐Reduction of Surface Hydroxyl
Authors: Zhao Yinghe , Gu Jinxing , Chen Zhongfang 
Published: August 2019

AbstractFe3GeTe2 is a water‐ and air‐stable, metallic, and layered material. Very recently, few‐layer and single‐layer Fe3GeTe2 have been successfully exfoliated from its bulk and revealed as 2D ferromagnets (Nature 2018, 563, 94; Nat. Mater. 2018, 17, 778). Here, the basal plane of Fe3GeTe2 is demonstrated to be of high electrocatalytic activity towards oxygen evolution reaction (OER) without resorting to any chemical modifications, by means of systematic density functional theory computations. The Fe3GeTe2 nanosheet preserves the metallic character of the bulk, and its 2D layered structure provides abundant exposed active sites to catalyze OER. All these unique characteristics suggest that the Fe3GeTe2 nanosheet may be an excellent catalyst for electrochemical OER. More importantly, it is found that the self‐reduction of surface hydroxyl into water can significantly reduce the overpotential for OER, which greatly boosts the OER activity. This work not only reveals new mechanisms for OER but also opens the door for the application of emerging 2D ferromagnets in the field of energy storage and conversion.
Avoidance of Catastrophic Structural Failure as an Evolutionary Constraint: Biomechanics of the Acorn Weevil Rostrum
Authors: Jansen Michael A. , Williams Jason , Chawla Nikhilesh , Franz Nico M. 
Published: August 2019

AbstractThe acorn weevil (Curculio Linnaeus, 1758) rostrum (snout) exhibits remarkable flexibility and toughness derived from the microarchitecture of its exoskeleton. Modifications to the composite profile of the rostral cuticle that simultaneously enhance the flexibility and toughness of the distal portion of the snout are characterized. Using classical laminate plate theory, the effect of these modifications on the elastic behavior of the exoskeleton is estimated. It is shown that the tensile behavior of the rostrum across six Curculio species with high morphological variation correlates with changes in the relative layer thicknesses and orientation angles of layers in the exoskeleton. Accordingly, increased endocuticle thickness is strongly correlated with increased tensile strength. Rostrum stiffness is shown to be inversely correlated with work of fracture; thus allowing a highly curved rostrum to completely straighten without structural damage. Finally, exocuticle rich invaginations of the occipital sutures are identified both as a likely site of crack initiation in tensile failure and as a source of morphological constraint on the evolution of the rostrum in Curculio weevils. It is concluded that avoidance of catastrophic structural failure, as initiated in these sutures under tension, is the driving selective pressure in the evolution of the female Curculio rostrum.
Healable and Mechanically Super‐Strong Polymeric Composites Derived from Hydrogen‐Bonded Polymeric Complexes
Authors: An Ni , Wang Xiaohan , Li Yixuan , Zhang Ling , Lu Zhongyuan , Sun Junqi 
Published: August 2019

AbstractIt is challenging to fabricate mechanically super‐strong polymer composites with excellent healing capacity because of the significantly limited mobility of polymer chains. The fabrication of mechanically super‐strong polymer composites with excellent healing capacity by complexing polyacrylic acid (PAA) with polyvinylpyrrolidone (PVPON) in aqueous solution followed by molding into desired shapes is presented. The coiled PVPON can complex with PAA in water via hydrogen‐bonding interactions to produce transparent PAA–PVPON composites homogenously dispersed with nanoparticles of PAA–PVPON complexes. As healable materials, the PAA–PVPON composite materials with a glass transition temperature of ≈107.9 °C exhibit a super‐high mechanical strength, with a tensile strength of ≈81 MPa and a Young's modulus of ≈4.5 GPa. The PAA–PVPON composites are stable in water because of the hydrophobic interactions among pyrrolidone groups. The super‐high mechanical strength of the PAA–PVPON composite materials originates from the highly dense hydrogen bonds between PAA and PVPON and the reinforcement of in situ formed PAA–PVPON nanoparticles. The reversibility of the relatively weak but dense hydrogen bonds enables convenient healing of the mechanically strong PAA–PVPON composite materials from physical damage to restore their original mechanical strength.
Ir‐catalyzed Asymmetric Hydrogenation of α‐Imino Esters with Chiral Ferrocenylphosphine‐Phosphoramidite Ligands
Authors: Hu Xin‐Hu , Hu Xiang‐Ping 
Published: August 2019

AbstractAn Ir‐catalyzed asymmetric hydrogenation of α‐imino esters with unsymmetrical hybrid chiral ferrocenylphosphine‐phosphoramidite ligands for the synthesis of optically active α‐aryl glycines has been described. The result indicated that the presence of the iodo‐substitutent at the 3/3’‐position of the binaphthyl unit of ligand could significantly improve the catalytic performance. This method features high asymmetric induction and reasonable functional group tolerance, thus providing a concise and efficient approach toward chiral α‐aryl glycine derivatives with up to 96% ee.magnified image
NaCa0.6V6O16·3H2O as an Ultra‐Stable Cathode for Zn‐Ion Batteries: The Roles of Pre‐Inserted Dual‐Cations and Structural Water in V3O8 Layer
Authors: Zhu Kaiyue , Wu Tao , Huang Kevin 
Published: August 2019

AbstractRechargeable aqueous batteries with Zn2+ as a working‐ion are promising candidates for grid‐scale energy storage because of their intrinsic safety, low‐cost, and high energy‐intensity. However, suitable cathode materials with excellent Zn2+‐storage cyclability must be found in order for Zinc‐ion batteries (ZIBs) to find practical applications. Herein, NaCa0.6V6O16·3H2O (NaCaVO) barnesite nanobelts are reported as an ultra‐stable ZIB cathode material. The original capacity reaches 347 mAh g−1 at 0.1 A g−1, and the capacity retention rate is 94% after 2000 cycles at 2 A g−1 and 83% after 10 000 cycles at 5 A g−1, respectively. Through a combined theoretical and experimental approach, it is discovered that the unique V3O8 layered structure in NaCaVO is energetically favorable for Zn2+ diffusion and the structural water situated between V3O8 layers promotes a fast charge‐transfer and bulk migration of Zn2+ by enlarging gallery spacing and providing more Zn‐ion storage sites. It is also found that Na+ and Ca2+ alternately suited in V3O8 layers are the essential stabilizers for the layered structure, which play a crucial role in retaining long‐term cycling stability.
Prognosis of patients with chronic myeloid leukemia presenting in advanced phase is defined mainly by blast count, but also by age, chromosomal aberrations and hemoglobin
Authors: Lauseker Michael , Bachl Katharina , Turkina Anna , Faber Edgar , Prejzner Witold , Olsson‐Strömberg Ulla , Baccarani Michele , Lomaia Elza , Zackova Daniela , Ossenkoppele Gert , Griskevicius Laimonas , Schubert‐Fritschle Gabriele , Sacha Tomasz , Heibl Sonja , Koskenvesa Perttu , Bogdanovic Andrija , Clark Richard E. , Guilhot Joelle , Hoffmann Verena S. , Hasford Joerg , Hochhaus Andreas , Pfirrmann Markus 
Published: August 2019

AbstractChronic myeloid leukemia (CML) is usually diagnosed in chronic phase, yet there is a small percentage of patients that is diagnosed in accelerated phase or blast crisis. Due to this rarity, little is known about the prognosis of these patients. Our aim was to identify prognostic factors for this cohort. We identified 283 patients in the EUTOS population‐based and out‐study registries that were diagnosed in advanced phase. Nearly all patients were treated with tyrosine kinase inhibitors. Median survival in this heterogeneous cohort was 8.2 years. When comparing patients with more than 30% blasts to those with 20‐29% blasts, the hazard ratio (HR) was 1.32 (95%‐confidence interval (CI): [0.7‐2.6]). Patients with 20‐29% blasts had a significantly higher risk than patients with less than 20% blasts (HR: 2.24, 95%‐CI: [1.2‐4.0], P = .008). We found that the blast count was the most important prognostic factor; however, age, hemoglobin, basophils and other chromosomal aberrations should be considered as well. The ELTS score was able to define two groups (high risk vs non‐high risk) with an HR of 3.01 (95%‐CI: [1.81‐5.00], P < .001). Regarding the contrasting definitions of blast crisis, our data clearly supported the 20% cut‐off over the 30% cut‐off in this cohort. Based on our results, we conclude that a one‐phase rather than a two‐phase categorization of de novo advanced phase CML patients is appropriate.
Too big or too thin? New Caledonian adolescents' perceptions of overweight and underweight
Authors: Frayon Stéphane , Wattelez Guillaume , Cavaloc Yolande , Cherrier Sophie , Lerrant Yannick , Galy Olivier 
Published: August 2019

AbstractObjectivesThe first aim was to examine New Caledonian adolescents' views of what constitutes an overweight or underweight person. The second aim was to assess whether an environment with a high prevalence of overweight is associated with different norms of overweight or underweight in this population.MethodsThe Stunkard Figure Rating Scale was used for a sample of 699 pluriethnic adolescents in New Caledonia. Body mass index (BMI) was assessed for each participant and weight status was determined. The factors associated with higher figure ratings were determined by linear regression modeling.ResultsMultilinear regression analysis indicated that gender (being male) and BMI were associated with higher rating scores to designate overweight. Moreover, higher BMI z‐scores were associated with higher underweight figure ratings. Ethnicity, area of residence, age, and socioeconomic status were not associated with higher ratings of body image.ConclusionsThese findings show that an environment with a high prevalence of overweight does not necessarily shift adolescent “norms,” contrary to visual normalization theory. These results should be taken into account in educational overweight prevention programs.
AHRR methylation predicts smoking status and smoking intensity in both saliva and blood DNA
Authors: Philibert Robert , Dogan Meeshanthini , Beach Steven R. H. , Mills James A. , Long Jeffrey D. 
Published: August 2019

AbstractMany existing DNA repositories do not have robust characterizations of smoking, while for many currently ongoing studies, the advent of vaping has rendered traditional cotinine‐based methods of determining smoking status unreliable. Previously, we have shown that methylation status at cg05575921 in whole blood DNA can reliably predict cigarette consumption. However, whether methylation status in saliva can be used similarly has yet to be established. Herein, we use DNA from 418 biochemically confirmed smokers or nonsmokers to compare and contrast the utility of cg05575921 in classifying and quantifying cigarette smoking. Using whole blood DNA, a model incorporating age, gender, and methylation status had a receiver operating characteristic (ROC) area under the curve (AUC) for predicting smoking status of 0.995 with a nonlinear demethylation response to smoking. Using saliva DNA, the ROC AUC for predicting smoking was 0.971 with the plot of the relationship of DNA methylation to daily cigarette consumption being very similar to that seen for whole blood DNA. The addition of information from another methylation marker designed to correct for cellular heterogeneity improved the AUC for saliva DNA to 0.981. Finally, in 31 subjects who reported quitting smoking 10 or more years previously, cg05575921 methylation was nonsignificantly different from controls. We conclude that DNA methylation status at cg05575921 in DNA from whole blood or saliva predicts smoking status and daily cigarette consumption. We suggest these epigenetic assessments for objectively ascertaining smoking status will find utility in research, clinical, and civil applications.
Synthesis, characterization, and electrochemistry of monophosphine‐containing diiron propane‐1,2‐dithiolate complexes related to the active site of [FeFe]‐hydrogenases
Authors: Lin Hui‐Min , Li Jian‐Rong , Mu Chao , Li Ao , Liu Xu‐Feng , Zhao Pei‐Hua , Li Yu‐Long , Jiang Zhong‐Qing , Wu Hong‐Ke 
Published: August 2019

Five monophosphine‐substituted diiron propane‐1,2‐dithiolate complexes as the active site models of [FeFe]‐hydrogenases have been synthesized and characterized. Reactions of complex [Fe2(CO)6{μ‐SCH2CH(CH3)S}] (1) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me3NO·2H2O gave the monophosphine‐substituted diiron complexes [Fe2(CO)5(L){μ‐SCH2CH(CH3)S}] [L = P(4‐C6H4CH3)3, 2; Ph2P(2‐C5H4N), 3; P(4‐C6H4Cl)3, 4; PPh3, 5; P(4‐C6H4F)3, 6] in 81%–94% yields. Complexes 2–6 have been characterized by elemental analysis, spectroscopy, and X‐ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H2 in the presence of HOAc.
Phytotoxic Diterpenoids from Plants and Microorganisms
Authors: Wei Wenjun , Li Ya , Li Hangying , Ma Kailiang , Wang Liudi , Gao Kun 
Published: August 2019

AbstractPhytotoxic natural products with either unique or various structures are one of the most abundant sources for the discovery of potential allelochemicals, natural herbicides, and plant growth regulators. Phytotoxic diterpenoids, a relatively large class of natural products, play an important role in the plant‐plant or plant‐microorganism interactions. This article argues that the phytotoxic diterpenoids isolated from the plants and microorganisms can either inhibit the seed germination and the growth of plant seedlings or lead to some disease symptoms on the tested plant tissues and plant seedlings.
Incidence, predictors, and outcomes of distal vessel expansion on follow‐up intravascular ultrasound after recanalization of chronic total occlusions using new‐generation drug‐eluting stents: Data from the CTO‐IVUS randomized trial
Authors: Hong Sung‐Jin , Kim Byeong‐Keuk , Kim Young‐Joo , Rha Seung‐Woon , Lee Seung‐Jin , Kim Hee‐Yeol , Choi Jin‐Ho , Ahn Chul‐Min , Kim Jung‐Sun , Ko Young‐Guk , Choi Doonghoon , Hong Myeong‐Ki , Jang Yangsoo 
Published: August 2019

AbstractObjectivesTo evaluate the incidence, predictors, and outcomes of distal vessel expansion on intravascular ultrasound (IVUS) after recanalization of chronic total occlusion (CTO) particularly using new‐generation drug‐eluting stent (DES).BackgroundThe luminal changes of narrowed vessels distal to CTO segments after recanalization using new‐generation DES have rarely been studied.MethodsThis substudy of the CTO‐IVUS (Chronic Total Occlusion InterVention with drUg‐eluting Stents) trial included a total of 69 new‐generation DES‐treated CTOs with serial matched IVUS analyses at index percutaneous coronary intervention (PCI) and at 1‐year follow‐up. The predictors of distal vessel expansion, any increase of lumen area at the distal reference (LAdistal) on 1‐year follow‐up IVUS, were evaluated by multivariable binary logistic analyses.ResultsDistal vessel expansion was identified in 46 (67%). Independent determinants of distal vessel expansion were proximal CTO, a smaller LAdistal at the index PCI, a greater minimal stent area‐to‐LAdistal (MSA‐to‐LAdistal) ratio, and a greater lumen area at the distal stent edge‐to‐LAdistal (LAedge‐to‐LAdistal) ratio. The cut‐off values of a MSA‐to‐LAdistal ratio and a LAedge‐to‐LAdistal ratio predicting the distal vessel expansion by receiver operating characteristic curve analysis were 1.0 and 1.1, respectively. During the median 5.1 years, rates of target vessel revascularization, cardiac death, and stent thrombosis were similar in the distal vessel‐expanded and nonexpanded groups.ConclusionAfter opening CTO with new‐generation DES, two‐thirds of patients exhibited distal vessel expansion on 1‐year follow‐up IVUS. Expansion determinants were a proximal CTO, lower LAdistal, and larger stent areas relative to the LAdistal (modifiable procedural predictors).
Electrochemical Reduction of CO2 on Nitrogen‐Doped Carbon Catalysts With and Without Iron
Authors: Silva Wanderson O. , Silva Gabriel C. , Webster Richard F. , Benedetti Tania M. , Tilley Richard D. , Ticianelli Edson A. 
Published: August 2019

AbstractThe carbon dioxide reduction reaction (CO2RR) catalyzed by N‐doped carbon materials was studied under operando conditions by on line differential electrochemical mass spectrometry and in‐line gas chromatography. Fe/NC electrocatalysts were synthesized by using a Fe+2‐impregnated pyridyl/triazine complex heat treated at 800 °C in nitrogen (Fe/NC(N2)) or ammonia (Fe/NC(NH3)) atmospheres; an iron‐free nitrogen‐doped carbon electrocatalyst (NC(NH3)) was also synthesized and included for comparison. Here, superior CO faradaic efficiencies were evidenced for NC(NH3) compared to Fe/NC(NH3), independently of the applied electrode potential; however, much larger overall catalytic activity for the promotion of the CO2RR and/or HER has been observed for Fe/NC(NH3), generating different stoichiometric ratios of syngas (CO/H2). Another important evidence is that N‐pyridinic groups, even in absence of Fe−N4 moieties and presence of high iron nanoparticles loading, play an important role as active sites for selective CO2 reduction to CO at low overpotentials.
Efficient Electrochemical Hydrogenation of 5‐Hydroxymethylfurfural to 2,5‐Bis(hydroxymethyl)furan on Ag‐Displaced Nanotextured Cu Catalysts
Authors: Zhang Lu , Zhang Fen , Michel Frederick C. , Co Anne C. 
Published: August 2019

AbstractInvited for this month's cover picture is the group of Dr. Anne C. Co (The Ohio State University, Ohio, USA). The cover picture shows the nanostructured AgCu catalyst used for the electrochemical hydrogenation of 5‐hydroxymethylfurfural (HMF), a bio‐based platform chemical, to 2,5‐bis(hydroxymethyl)furan (BHMF), a building block for polymers. Read the full text of the Article at 10.1002/celc.201900640.
Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]− Building Block Via Solid‐State NMR Spectroscopy, Polarized Neutron Diffraction, and First‐Principle Calculations
Authors: De Siddhartha , Flambard Alexandrine , Garnier Delphine , Herson Patrick , Köhler Frank H. , Mondal Abhishake , Costuas Karine , Gillon Béatrice , Lescouëzec Rodrigue , Le Guennic Boris , Gendron Frédéric 
Published: August 2019

AbstractThe local magnetic structure in the [FeIII(Tp)(CN)3]− building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first‐principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin‐density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin‐polarization on the carbon atoms and spin‐delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab‐initio calculations allowed us to connect the experimental spin‐density map characterized by PND and the suggested distribution of the spin‐density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo‐contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point‐dipole model. These discrepancies underline the limitation of the point‐dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo‐contact contributions.
Ammonia Synthesis through Hydrolysis of a Trianionic Pincer Ligand‐Supported Molybdenum–Nitride Complex
Authors: Chakraborty Jhonti , Mandal Ushnish , Ghiviriga Ion , Abboud Khalil A. , Veige Adam S. 
Published: August 2019

AbstractReported is the hydrolysis of a homogeneous Mo‐nitride complex bearing a trianionic pincer‐type ligand to produce ammonia. Treating the anionic [(ONO)]Mo≡N(OtBu)]Ph3PCH3 with two equivalents of water produces ammonia and the dioxo complex [(ONO)]MoO2]Ph3PCH3. X‐Ray crystal structures of the starting nitrido complex and product dioxo complex are presented. Evidence for ammonia release comes from GC‐MS and deuterium‐labelling studies. The reaction is presented in the context of a two‐stage solar thermochemical dinitrogen fixation process as the solid‐state nitride hydrolysis step.
Concurrent use of opioids with benzodiazepines or nonbenzodiazepine sedatives among patients with cancer referred to an outpatient palliative care clinic
Authors: Haider Ali , Azhar Ahsan , Nguyen Kristy , Dev Rony , Naqvi Syed Mujtaba Ali , Naqvi Syed Mussadiq Ali , Edwards Tonya , Reddy Akhila , Dalal Shalini , Tanco Kimberson C. , Arthur Joseph , Williams Janet L. , Park Minjeong , Liu Diane D. , Dibaj Seyedeh S. , Bruera Eduardo 
Published: August 2019

BackgroundThe concurrent use of opioids with benzodiazepines (BZD) or nonbenzodiazepine sedatives (S) recently was found to be associated with an increased risk of overdose death compared with the use of opioids alone. In the current study, the authors examined the frequency and trend of concurrent opioid/BZD‐S use and its associated risk factors among patients with cancer.MethodsData regarding the frequency and trend of concurrent opioid/BZD‐S use were extracted for 1500 randomly selected patients referred to the outpatient palliative care clinic at The University of Texas MD Anderson Cancer Center between the calendar years of 2011 and 2016. To explore associated risk factors, the authors compared the demographic and clinical predictors of 418 patients each in the concurrent opioid/BZD‐S group and opioids‐only group.ResultsIn 2011, at the time of referral to the palliative care clinic, 96 of 221 patients with cancer (43%) were prescribed concurrent opioids/BZD‐S. This rate progressively declined to 67 of 217 patients (31%) by 2016 (P = .0008). Patients in the concurrent opioid/BZD‐S group had a higher percentage of females (233 individuals; 55% [P = .007]) and whites (323 individuals; 77% [P = .002]), and patients reported higher scores regarding depression (P = .0001), anxiety (P ≤ .0001), drowsiness (P = .048), and worst feeling of well‐being (P = .001). The morphine equivalent daily dose was significantly higher in concurrent opioid/BZD‐S group (median of 67.5 mg/day [interquartile range (IQR), 30‐135 mg/day] vs 60 mg/day [IQR, 30‐105 mg/day]; P = .034). Multivariate analysis demonstrated that anxiety (P ≤ .0001), white race (P = .0092), and poor Eastern Cooperative Oncology Group performance status (P = .0017) were significantly associated with concurrent use.ConclusionsThe concurrent use of opioids with BZD‐S has declined but continues to be frequent among patients with cancer. Anxiety, white race, and poor Eastern Cooperative Oncology Group performance status were associated with its use. More research is needed to explore which medications can replace these agents.