bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hexagonal Sphericon Hematite with High Performance for Water Oxidation
Authors: Odedairo Taiwo , Yan Xuecheng , Yao Xiangdong , Ostrikov Kostya (Ken) , Zhu Zhonghua 
Published: October 2017

AbstractA cost‐effective hexagonal sphericon hematite with predominant (110) facets for the oxygen evolution reaction (OER) is demonstrated. Sequential incorporation of near‐atomic uniformly distributed Ce species and Ni nanoparticles into selected sites of the hematite induces a complex synergistic integration phenomenon that enhances the overall catalytic OER performance. This cheap hexagonal sphericon hematite (Fe ≈ 98%) only needs a small overpotential (η) of 0.34 V to reach 10 mA cm−2, superior to commercial IrO2 and more expensive Co‐, Ni‐, and Li‐based electrocatalysts.
Visible light induced Trifluoromethyl Migration: Easy Access to α‐Trifluoromethylated Ketones from Enol Triflates
Authors: Liu Shuyang , Jie Jiyang , Yu Jipan , Yang Xiaobo 
Published: October 2017

AbstractHerein, we reported a novel method to synthesize α‐trifluoromethylated ketones from enol triflates. Involving a cascade sulfur dioxide extrusion and a CF3 (trifluoromethyl) radical addition process, this reaction proceeds at room temperature and is driven by visible light irradiation. This protocol bears good functional group compatibility, which can generate the desired products in good to excellent yields even in gram scale. It is hoped that this approach to generate CF3 radicals from enol triflates can be used in other radical‐involved reactions.magnified image
Lemierre's syndrome presented with acute pancreatitis
Authors: Garcia Laura , Ito Kaori 
Published: October 2017

CaseLemierre's syndrome is a rare clinical condition that is characterized by infected internal jugular vein thrombosis with metastatic septicemia. The most common causative agent is Fusobacterium necrophorum. A previously healthy 37‐year‐old woman presented to our emergency department with nausea, vomiting, and diarrhea. She was admitted to the general practice unit with a diagnosis of acute pancreatitis then was subsequently transferred to the intensive care unit due to shock. Physical examination revealed tenderness on right side of the neck. Blood cultures were remarkable for F. necrophorum. Clinical symptoms led to subsequent ultrasound and computed tomography scan of the neck, confirming internal jugular vein thrombosis.OutcomeThe patient was treated with antibiotics for 6 weeks. Anticoagulation therapy was initiated.ConclusionWe report a case of Lemierre's syndrome that presented as acute pancreatitis. The high index of suspicion of this disease is important for early diagnosis.
Catalytic Hydroalkylation of Allenes
Authors: Lee Mitchell , Nguyen Mary , Brandt Chance , Kaminsky Werner , Lalic Gojko 
Published: October 2017

AbstractWe have developed a catalytic method for the hydroalkylation of allenes using alkyl triflates as electrophiles and silane as a hydride source. The reaction has an excellent substrate scope and is compatible with a wide range of functional groups, including esters, aryl halides, aryl boronic esters, sulfonamides, alkyl tosylates, and alkyl bromides. We found evidence for a reaction mechanism that involves unusual dinuclear copper ally complexes as catalytic intermediates. The unusual structure of these complexes provides a rationale for their unexpected reactivity.
Creation of “Rose Petal” and “Lotus Leaf” Effects on Alumina by Surface Functionalization and Metal‐Ion Coordination
Authors: Mukhopadhyay Rahul Dev , Vedhanarayanan Balaraman , Ajayaghosh Ayyappanpillai 
Published: October 2017

AbstractFunctional differences between superhydrophobic surfaces, such as lotus leaf and rose petals, are due to the subtle architectural features created by nature. Mimicry of these surfaces with synthetic molecules continues to be fascinating as well as challenging. Herein, we demonstrate how inherently hydrophilic alumina surface can be modified to give two distinct superhydrophobic behaviors. Functionalization of alumina with an organic ligand resulted in a rose‐petal‐like surface (water pinning) with a contact angle of 145° and a high contact angle hysteresis (±69°). Subsequent interaction of the ligand with Zn2+ resulted in a lotus‐leaf‐like surface with water rolling behavior owing to high contact angle (165°) and low‐contact‐angle‐hysteresis (±2°). In both cases, coating of an aromatic bis‐aldehyde with alkoxy chain substituents was necessary to emulate the nanowaxy cuticular feature of natural superhydrophobic materials.
A De Novo Heterodimeric Due Ferri Protein Minimizes the Release of Reactive Intermediates in Dioxygen‐Dependent Oxidation
Authors: Chino Marco , Leone Linda , Maglio Ornella , D'Alonzo Daniele , Pirro Fabio , Pavone Vincenzo , Nastri Flavia , Lombardi Angela 
Published: October 2017

AbstractMetalloproteins utilize O2 as an oxidant, and they often achieve a 4‐electron reduction without H2O2 or oxygen radical release. Several proteins have been designed to catalyze one or two‐electron oxidative chemistry, but the de novo design of a protein that catalyzes the net 4‐electron reduction of O2 has not been reported yet. We report the construction of a diiron‐binding four‐helix bundle, made up of two different covalently linked α2 monomers, through click chemistry. Surprisingly, the prototype protein, DF‐C1, showed a large divergence in its reactivity from earlier DFs (DF: due ferri, two iron). DFs release the quinone imine and free H2O2 in the oxidation of 4‐aminophenol in the presence of O2, whereas FeIII‐DF‐C1 sequesters the quinone imine into the active site, and catalyzes inside the scaffold an oxidative coupling between oxidized and reduced 4‐aminophenol. The asymmetry of the scaffold allowed a fine‐engineering of the substrate binding pocket, that ensures selectivity.
Changes in Koppen–Trewartha climate classification over South America from RegCM4 projections
Authors: Fernandez Julio P. R. , Franchito Sergio H. , Rao V. Brahmananda , Llopart Marta 
Published: October 2017

AbstractThe Koppen–Trewartha (K–T) classification is used to investigate the biomes change in the future climate over South America (SA). For the middle (2035–2060) and end (2075–2100) of the 21st century mean ensemble of Regional Climate Model version 4 simulations for the Representative Concentration Pathway 8.5 scenario are presented. The global‐coupled models of Coupled Model Intercomparison Project Phase 5 drive the members for the period 1970–2100 using different physics configurations. The delta change approach is applied to filter out the bias of the model simulation. Notable changes of the K–T climates are found in SA, mainly in Brazil. Replacement of tropical wet‐dry (Aw) by dry semiarid (Bs) occurs over Northeast Brazil (NEB). Reduction of tropical humid (Ar) and an increase of Aw is projected in the North Brazil and Amazon. Retreat of subtropical humid (Cr) replaced by Aw is found in the Southeast Brazil. An increase of subtropical winter‐dry (Cw) and decrease Cr is noted in Argentina and in Paraguay Cr is replaced by Ar. In the south of SA, a retreat of subarctic oceanic (Eo) and an increase of temperate oceanic (Do) and dry arid (Bw) occur. In general, the projected changes of K–T climate types in the 21st century over SA show a tendency for a drier climate.
Sensorimotor learning and associated visual perception are intact but unrelated in autism spectrum disorder
Authors: Hayes Spencer J. , Andrew Matthew , Foster Nathan C. , Elliott Digby , Gowen Emma , Bennett Simon J. 
Published: October 2017

Humans show an astonishing capability to learn sensorimotor behaviours. However, data from sensorimotor learning experiments suggest the integration of efferent sensorimotor commands, afferent sensorimotor information, and visual consequences of a performed action during learning is different in autism, leading to atypical representation of internal action models. Here, we investigated the generalization of a sensorimotor internal action model formed during sensorimotor learning to a different, but associated, visual perception task. Although motor timing was generally less accurate in adults with autism, following practice with feedback both autistic adults, and controls, significantly improved performance of the movement sequence timing task by reducing timing error. In a subsequent perception task, both groups demonstrated similar temporal‐discrimination accuracy (autism = 75%; control = 76%). Significant correlations between motor timing error, and temporal‐discrimination during a perception task, was found for controls. No significant correlations were found for autistic adults. Our findings indicate that autistic adults demonstrated adaptation by reducing motor timing error through sensorimotor learning. However, the finding of significant correlations between motor timing error and temporal‐discrimination accuracy in the control group only suggests sensorimotor processes underpinning internal action model formation operate differently in autism. Autism Res 2018, 11: 296–304. © 2017 International Society for Autism Research, Wiley Periodicals, Inc.Lay SummaryWe showed autistic adults learned a new motor skill, and visually judged moving objects, to a similar level of accuracy as a control group. Unlike the control group, there was no relationship between how well autistic adults learned the motor skill, and how well they judged objects. The lack of a relationship might be one of the reasons autistic adults interact differently in the social world.
HBxAg suppresses cell apoptosis and promotes the secretion of placental hormones in human placental trophoblasts via activation of the EGFR/Akt pathway
Authors: Wang Weimin , Bai Guiqin , Zhang Yuting , Zhang Ting , Li Chen , Yuan Yongxing , Liu Sixue , Wang Caili 
Published: October 2017

AbstractThe aim of this study is to investigate the role of Hepatitis B virus x (HBx) in the growth and secretion of human placental trophoblasts. Firstly, placenta tissues were collected from pregnant HBV carriers with various viral loads. The results of immunohistochemical technique showed that the HBx protein and pEGFR protein levels were both markedly increased with the viral load elevation. Then, a placental trophoblast cell strain (JEG‐3‐HBx), which stably expressed HBx mRNA and protein, was established with the pcDNA‐HBx transfection followed by the G418 selection. The JEG‐3‐HBx strain displayed distinct activation of the EGFR/AKT pathway, a lower level of cell apoptosis, and higher secretion levels of placental hormones, including human chorionic gonadotropin (hCG), progesterone, estrogen and β‐endorphin. Subsequently, HBx siRNA was used to silence the HBx gene in the JEG‐3‐HBx strain. Our data showed that the HBx siRNA transfection markedly suppressed the activation of the EGFR/AKT pathway, promoted cell apoptosis, and reduced the secretion of the placental hormones. Finally, EGF was applied to simulate the JEG‐3‐HBx strain with or without the HBx siRNA transfection. EGF treatment counteracted the reduction of cell apoptosis and the suppression of hormone secretion caused by HBx siRNA in the cell strain. In conclusion, the pEGFR protein was robustly upregulated in HBx‐infected human placenta tissues and trophoblast cells. HBx reduces cell apoptosis and promotes the secretion of placental hormones in human placental trophoblast cells via activation of the EGFR/Akt pathway.
Carnosine and N‐acetyl cysteine protect against sodium nitrite‐induced oxidative stress in rat blood
Authors: Ansari Fariheen Aisha , Mahmood Riaz 
Published: October 2017

AbstractSodium nitrite (NaNO2) is widely used in the food industry as a preservative and colorant in meat and fish products. Industrialization and improper agricultural practices have greatly increased human exposure to high nitrite levels, mainly through contaminated drinking water, causing various health disorders. We have investigated the protective effect of carnosine (CAR) and N‐acetyl cysteine (NAC) on NaNO2‐induced toxicity in rat blood. CAR is a bioactive dipeptide found in mammalian muscle while NAC is a synthetic sulfhydryl amino acid and an important precursor of glutathione. Animals were given a single acute oral dose of NaNO2 at 60 mg/kg body weight with or without prior administration of either CAR or NAC. Rats were sacrificed after 24 h, blood was withdrawn and plasma and erythrocytes were isolated. Administration of NaNO2 alone increased methemoglobin levels and methemoglobin reductase activity, decreased the activities of antioxidant defense and metabolic enzymes and significantly weakened the total antioxidant capacity of rat erythrocytes. Similar effects were seen in plasma of NaNO2‐treated rats. In contrast, administration of CAR or NAC, prior to NaNO2 treatment, markedly attenuated the NaNO2‐elicited deleterious effects. Thus, CAR and NAC can mitigate nitrite‐induced metabolic alterations and oxidative damage probably due to their intrinsic biochemical antioxidant properties. This study suggests that CAR and NAC can be potentially used as therapeutic/protective agents against NaNO2 toxicity.
Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMenPh(3−n))4]
Authors: Funes‐Ardoiz Ignacio , Nelson David J. , Maseras Feliu 
Published: October 2017

AbstractDensity functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMenPh(3−n))4], revealing the crucial role of an open‐shell singlet transition state for halide abstraction. The formation of NiI versus NiII has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMenPh(3−n))3], via an open‐shell singlet transition state; (ii) SN2‐type oxidative addition to [Ni(PMenPh(3−n))3], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMenPh(3−n))2]. For the overall reaction between [Ni(PMe3)4], PhCl, and PhI, a microkinetic model was used to show that our results are consistent with the experimentally observed ratios of NiI and NiII when the PEt3 complex is used. Importantly, [Ni(PMenPh(3−n))2] complexes often have little, if any, role in oxidative addition reactions because they are relatively high in energy. The behaviour of [Ni(PR3)4] complexes in catalysis is therefore likely to differ considerably from those based on diphosphine ligands in which two coordinate Ni0 complexes are the key species undergoing oxidative addition.
Molecular Switches for any pH: A Systematic Study of the Versatile Coordination Behaviour of Cyclam Scorpionands
Authors: Lau Yu Heng , Clegg Jack K. , Price Jason R. , Macquart Rene B. , Todd Matthew H. , Rutledge Peter J. 
Published: October 2017

AbstractMolecular switches have many potential applications in nanoscience and biomedicine. Transition metal complexes that can be switched from an inert, unreactive state to a catalytically active one by a simple change in conditions (e.g. pH shift) or by binding to a specific biomolecular target—so‐called target‐activated metal complexes (TAMCs)—hold particular allure as a means of harnessing the potent but at times indiscriminate reactivity of metal‐based drugs. Towards this goal, we have prepared a series of ten structurally related ligands, each of which bears a different pendant side‐arm functional group appended to a common macrocyclic core, along with copper(II) and nickel(II) complexes of these cyclam‐based “molecular scorpionands”. X‐ray crystal structures reveal a variety of binding modes between pendant side‐arm and metal centre that depend on the constituent donor atoms. To investigate the switchability of side‐arm coordination in solution, spectrophotometric pH titrations were carried out for all 20 metal complexes. The majority of the complexes undergo spectroscopic changes that are consistent with a switch in pendant coordination state at a specific pH. This ligand series represents a comprehensive model platform from which to build pH‐switchable metal complexes for applications in nanoscience and biomedicine.
Optimal Design of Experiments Based on Bootstrapping
Authors: Paquet‐Durand Olivier , Hitzmann Bernd 
Published: October 2017

AbstractIn diesem Beitrag wird gezeigt, dass eine optimale Versuchsplanung zur Bestimmung kinetischer Parameter mittels Bootstrapping in moderater Zeit durchgeführt werden kann. Als Beispielsystem dient hier eine Folgereaktion erster Ordnung. Bootstrapping zur Parameterfehlerschätzung ist zwar signifikant rechenaufwändiger, bietet aber gegenüber der klassischen Methode, basieren auf der Fisher‐Information, den Vorteil, dass die Wahrscheinlichkeitsdichteverteilungen der Parameter nicht als normalverteilt angenommen werden müssen. Auch die Messfehler müssen für Bootstrapping nicht bekannt sein.
Radiation therapy utilization in Medicare beneficiaries with early‐stage breast cancer
Authors: Wallace Audrey S. , Keene Kimberley S. , Williams Courtney P. , Jackson Bradford E. , Pisu Maria , Partridge Edward E. , Rocque Gabrielle B. 
Published: October 2017

BACKGROUNDThere is increasing evidence that radiation therapy (RT) can be omitted for select older patients who are compliant with hormonal blockade, but there is no recent claim‐based analysis for determining patterns of care and guiding possible treatment recommendations.METHODSMedicare beneficiaries who were 65 years old or older and were diagnosed with breast cancer at 1 of 12 cancer centers affiliated with an academic center in the southeastern United States were analyzed. Stage 0 or I patients treated with lumpectomy from 2012 to 2014 were identified. Patient, treatment, and center characteristics were analyzed for the utilization of RT.RESULTSAmong 800 women treated with lumpectomy, 64% received adjuvant radiation. The median age was 74 years. The omission of RT was more likely in older patients, stage 0 patients, and patients with more comorbidities (P < .01). Hormonal blockade was used in 41% of the patients who did not receive RT. The utilization of hormonal blockade with the omission of RT was more likely in patients with fewer comorbidities (P < .01).CONCLUSIONSIn an older cohort of patients who otherwise would have qualified for the omission of radiation, two‐thirds were treated with radiation. Future guideline recommendations should address omission in the context of hormonal blockade compliance because only 41% of the patients used hormonal blockade when radiation was not delivered. Cancer 2018;124:475‐81. © 2017 American Cancer Society.
Distinct pattern of TP53 mutations in human immunodeficiency virus–related head and neck squamous cell carcinoma
Authors: Gleber‐Netto Frederico O. , Zhao Mei , Trivedi Sanchit , Wang Jiping , Jasser Samar , McDowell Christina , Kadara Humam , Zhang Jiexin , Wang Jing , William William N. , Lee J. Jack , Nguyen Minh Ly , Pai Sara I. , Walline Heather M. , Shin Dong M. , Ferris Robert L. , Carey Thomas E. , Myers Jeffrey N. , Pickering Curtis R. ,   for the Head and Neck Cancer Specialized Program of Research Excellence (SPORE) Human Immunodeficiency Virus (HIV) Supplement Consortium
Published: October 2017

BACKGROUNDHuman immunodeficiency virus–infected individuals (HIVIIs) have a higher incidence of head and neck squamous cell carcinoma (HNSCC), and clinical and histopathological differences have been observed in their tumors in comparison with those of HNSCC patients without a human immunodeficiency virus (HIV) infection. The reasons for these differences are not clear, and molecular differences between HIV‐related HNSCC and non–HIV‐related HNSCC may exist. This study compared the mutational patterns of HIV‐related HNSCC and non–HIV‐related HNSCC.METHODSThe DNA of 20 samples of HIV‐related HNSCCs and 32 samples of non–HIV‐related HNSCCs was sequenced. DNA libraries covering exons of 18 genes frequently mutated in HNSCC (AJUBA, CASP8, CCND1, CDKN2A, EGFR, FAT1, FBXW7, HLA‐A, HRAS, KEAP1, NFE2L2, NOTCH1, NOTCH2, NSD1, PIK3CA, TGFBR2, TP53, and TP63) were prepared and sequenced on an Ion Personal Genome Machine sequencer. DNA sequencing data were analyzed with Ion Reporter software. The human papillomavirus (HPV) status of the tumor samples was assessed with in situ hybridization, the MassARRAY HPV multiplex polymerase chain reaction assay, and p16 immunostaining. Mutation calls were compared among the studied groups.RESULTSHIV‐related HNSCC revealed a distinct pattern of mutations in comparison with non–HIV‐related HNSCC. TP53 mutation frequencies were significantly lower in HIV‐related HNSCC. Mutations in HIV+ patients tended to be TpC>T nucleotide changes for all mutated genes but especially for TP53.CONCLUSIONSHNSCC in HIVIIs presents a distinct pattern of genetic mutations, particularly in the TP53 gene. HIV‐related HNSCC may have a distinct biology, and an effect of the HIV virus on the pathogenesis of these tumors should not be ruled out. Cancer 2018;124:84‐94. © 2017 American Cancer Society.
A combination of MTAP and BAP1 immunohistochemistry in pleural effusion cytology for the diagnosis of mesothelioma
Authors: Kinoshita Yoshiaki , Hida Tomoyuki , Hamasaki Makoto , Matsumoto Shinji , Sato Ayuko , Tsujimura Tohru , Kawahara Kunimitsu , Hiroshima Kenzo , Oda Yoshinao , Nabeshima Kazuki 
Published: October 2017

BACKGROUNDHomozygous deletion of 9p21 detected by fluorescence in situ hybridization (FISH) and loss of BRCA1‐associated protein 1 (BAP1) expression detected by immunohistochemistry (IHC) are useful for the differentiation between malignant pleural mesothelioma (MPM) and reactive mesothelial hyperplasia. The authors previously described that IHC expression of the protein product of the methylthioadenosine phosphorylase (MTAP) gene, which is localized in the 9p21 chromosomal region, was correlated with the deletion status of 9p21 FISH in MPM tissues. In the current study, the authors investigated whether a combination of MTAP and BAP1 IHC could distinguish MPM from reactive mesothelial cells (RMC) in cell blocks obtained from pleural effusions.METHODSThe authors examined IHC expression of MTAP and BAP1 in cell blocks obtained from pleural effusions of 45 cases of MPM and 21 cases of reactive mesothelial hyperplasia. Furthermore, IHC expression of MTAP was compared with the deletion status of 9p21 FISH.RESULTSMTAP and BAP1 IHC differentiated MPM from RMC with 100% specificity for both and sensitivities of 42.2% and 60.0%, respectively. The combination of MTAP and BAP1 IHC yielded a sensitivity of 77.8%, which was higher than that of BAP1 IHC alone or 9p21 FISH alone (62.2%). Moreover, a high degree of concordance was observed between the results of MTAP IHC and 9p21 FISH in cell blocks.CONCLUSIONSA combination of MTAP and BAP1 IHC in cell blocks from pleural effusions appears to be a reliable and useful method for differentiating MPM cells from RMC and can be used in the routine diagnosis of MPM. Cancer Cytopathol 2018;126:54–63. © 2017 American Cancer Society.