bluuebunny/crossref_metadata_2025_split huggingface dataset:
Experimentally Calibrated Analysis of the Electronic Structure of CuO+: Implications for Reactivity
Authors: Srnec Martin , Navrátil Rafael , Andris Erik , Jašík Juraj , Roithová Jana 
Published: November 2018

AbstractThe CuO+ core is a central motif of reactive intermediates in copper‐catalysed oxidations occurring in nature. The high reactivity of CuO+ stems from a weak bonding between the atoms, which cannot be described by a simple classical model. To obtain the correct picture, we have investigated the acetonitrile‐ligated CuO+ ion using neon‐tagging photodissociation spectroscopy at 5 K. The spectra feature complex vibronic absorption progressions in NIR and visible regions. Employing Franck–Condon analyses, we derived low‐lying triplet potential energy surfaces that were further correlated with multireference calculations. This provided insight into the ground and low‐lying excited electronic states of the CuO+ unit and elucidated how these states are perturbed by the change in ligation. Thus, we show that the bare CuO+ ion has prevailingly a copper(I)‐biradical oxygen character. Increasing the number of ligands coordinated to copper changes the CuO+ character towards the copper(II)‐oxyl radical structure.
Bioinspired Radical Stetter Reaction: Radical Umpolung Enabled by Ion‐Pair Photocatalysis
Authors: Morack Tobias , Mück‐Lichtenfeld Christian , Gilmour Ryan 
Published: November 2018

AbstractA bioinspired, intermolecular radical Stetter reaction of α‐keto acids and aldehydes is disclosed that is contingent on a formal “radical umpolung” concept. Enabled by secondary amine activation, electrostatic recognition ensures that the α‐ketocarboxylic acids, which function as latent acyl radicals, are proximal to the in situ generated iminium salts. This photoactive contact ion pair is an electron donor–acceptor (EDA) complex, and undergoes facile single electron transfer (SET) and rapid decarboxylation prior to radical–radical recombination. Importantly, decarbonylation is mitigated by this strategy. The initial computational validation on which the process is predicated matches closely with experiment. Synergising organo‐ and photocatalysis activation principles finally expands the mechanistic and synthetic scope of the classic Stetter reaction to include α,β‐unsaturated aldehydes as acceptors.
A Branched Diterpene Cascade: The Mechanism of Spinodiene Synthase from Saccharopolyspora spinosa
Authors: Rinkel Jan , Lauterbach Lukas , Dickschat Jeroen S. 
Published: November 2018

AbstractA diterpene synthase from Saccharopolyspora spinosa was found to convert geranylgeranyl diphosphate into the new natural products spinodiene A and B, accompanied by 2,7,18‐dolabellatriene. The structures and the formation mechanism of the enzyme products were investigated by extensive isotopic labelling experiments, which revealed an unusual branched isomerisation mechanism towards the neutral intermediate 2,7,18‐dolabellatriene. A Diels–Alder reaction was used to convert the main diterpene product with its rare conjugated diene moiety into formal sesterterpene alcohols.
Proteomics as a tool for tapping potential of entomopathogens as microbial insecticides
Authors: Harith Fadzilah Nazmi , Abdul‐Ghani Idris , Hassan Maizom 
Published: November 2018

AbstractBiopesticides are collective pest control harnessing the knowledge of the target pest and its natural enemies that minimize the risks of synthetic pesticides. A subset of biopesticides; bioinsecticides, are specifically used in controlling insect pests. Entomopathogens (EPMs) are micro‐organisms sought after as subject for bioinsecticide development. However, lack of understanding of EPM mechanism of toxicity and pathogenicity slowed the progress of bioinsecticide development. Proteomics is a useful tool in elucidating the interaction of entomopathogenic fungi, entomopathogenic bacteria, and entomopathogenic virus with their target host. Collectively, proteomics shed light onto insect host response to EPM infection, mechanism of action of EPM’s toxic proteins and secondary metabolites besides characterizing secreted and membrane‐bound proteins of EPM that more precisely describe relevant proteins for host recognition and mediating pathogenesis. However, proteomics requires optimized protein extraction methods to maximize the number of proteins for analysis and availability of organism's genome for a more precise protein identification.
Creativity: Past, present, and future
Authors: Mehta Ravi , Dahl Darren W. 
Published: November 2018

AbstractOur understanding of creativity has come a long way from when it was considered to be a mystical power. Indeed, creativity has grown into a defined cognitive process that can be influenced by a diverse range of internal and external factors. This article begins with a brief discussion of the history of creativity as a psychological construct and then outlines more recent work in the area, particularly focusing on how our understanding of creativity has been expanded in the last decade. In doing so, we explicate four defining factors that have been shown to play a critical role in shaping consumer creativity: cognitive ability, motivation, social‐personality, and environment. The article concludes with a discussion of three topics that we believe hold promise for future research efforts in the area.
Patterns and predictors of end‐of‐life care in older patients with pancreatic cancer
Authors: Nipp Ryan D. , Tramontano Angela C. , Kong Chung Yin , Hur Chin 
Published: November 2018

AbstractBackgroundLittle is known about end‐of‐life care among patients with pancreatic adenocarcinoma (PDAC). We used the Surveillance, Epidemiology, and End Results‐Medicare linked database to analyze patterns of hospice use and end‐of‐life treatment in patients with PDAC.MethodsWe included patients diagnosed with PDAC between 2000‐2011 and who had died by December 31, 2012. We assessed patterns of hospice use, chemotherapy receipt, and intensive care unit (ICU) admissions at end‐of‐life. We used multivariable logistic regression to investigate predictors of end‐of‐life care.ResultsIn our cohort of 16 309 patients, 70.5% enrolled in hospice, of which 29.1% enrolled in the last 7 days of life. Use of hospice increased over time, from 61.6% in 2000 to 77.5% in 2012 (P‐value for trend <0.0001). Among the entire cohort, 6.4% received chemotherapy within the last 14 days of life and 13.1% were admitted to the ICU within the last 30 days of life. Late ICU admissions increased over time, while chemotherapy receipt at the end‐of‐life decreased. Patients who were older, female, with higher SES, or from the South or Midwest were more likely to enroll in hospice. Those who were younger or male were more likely to receive chemotherapy or have an ICU admission at the end‐of‐life.ConclusionAlthough hospice enrollment has increased among patients with PDAC, late enrollment still occurs in a substantial proportion of patients. While chemotherapy at the end‐of‐life has decreased slightly, ICU admissions at the end‐of‐life have continued to increase. Further research is needed to determine effective ways of enhancing end‐of‐life care for patients with PDAC.
Ni/LnOx Catalysts (Ln=La, Ce or Pr) for CO2 Methanation
Authors: Alcalde‐Santiago Virginia , Davó‐Quiñonero Arantxa , Lozano‐Castelló Dolores , Quindimil Adrián , De‐La‐Torre Unai , Pereda‐Ayo Beñat , González‐Marcos José A. , González‐Velasco Juan R. , Bueno‐López Agustín 
Published: November 2018

AbstractThe effect of the LnOx support has been studied for Ni‐based CO2 methanation catalysts. 10 wt.% nickel catalysts with LaOx, CeO2 and PrOx supports have been prepared, characterized by N2 adsorption, XRD, XRF, TG‐MS (N2‐TPD and H2‐TPR) and XPS, and have been tested for CO2 methanation. The catalytic activity follows the trend Ni/CeO2>Ni/PrOx≫Ni/LaOx, all catalysts being very selective towards CH4 formation. The activity depends both on the nature of the catalytic active sites and on the stability of the surface CO2 and H2O species. Ni/CeO2 is the most active catalyst because (i) the Ni2+‐ceria interaction leads to the formation of the highest population of active sites for CO2 dissociation, (ii) the reduced Ni0 sites where H2 dissociation takes place are the most electronegative and active, and (iii) the stability of surface CO2 and H2O species is lowest. Ni/LaOx achieves lower activity because of the strong chemisorption of H2O and CO2, which poison the catalyst surface, and because this support is not able to promote the formation of highly active sites for CO2 and H2 dissociation. The behavior of Ni/PrOx is intermediate, being slightly lower to that of Ni/CeO2 because the formation of active sites is not so efficient and because the stability of chemisorbed CO2 is slightly higher.
Fluidization Behavior of Cohesive Ca(OH)2 Powders Mixed with Hydrophobic Silica Nanoparticles
Authors: Amjadi Omid , Tahmasebpoor Maryam , Aghdasinia Hassan 
Published: November 2018

AbstractDry mixing with hydrophobic silica nanopowders was used to improve the fluidization quality of Ca(OH)2 particles which belong to the Geldart C group and, thus, normally cannot be fluidized. Three parameters, i.e., sieved size of Ca(OH)2 particles and sieved size and weight percentage of SiO2 nanoparticles were selected for experiments. A direct proportionality was found between the coverage quality of materials over each other and the fluidization behavior of their corresponding adsorbents. Optimum SiO2 size and concentration values were determined for the improvement of Ca(OH)2 fluidizability. The sieved size of Ca(OH)2 powder had no consequential effect on the coverage quality. The Richarson‐Zaki equation and fractal analysis combined with a modified Richardson‐Zaki approach were proposed for prediction of the fluidization quality and agglomerate size.
Mercury(II) Binding to Metallothionein in Mytilus edulis revealed by High Energy‐Resolution XANES Spectroscopy
Authors: Manceau Alain , Bustamante Paco , Haouz Ahmed , Bourdineaud Jean Paul , Gonzalez‐Rey Maria , Lemouchi Cyprien , Gautier‐Luneau Isabelle , Geertsen Valérie , Barruet Elodie , Rovezzi Mauro , Glatzel Pieter , Pin Serge 
Published: November 2018

AbstractOf all divalent metals, mercury (HgII) has the highest affinity for metallothioneins. HgII is considered to be enclosed in the α and β domains as tetrahedral α‐type Hg4Cys11‐12 and β‐type Hg3Cys9 clusters similar to CdII and ZnII. However, neither the four‐fold coordination of Hg nor the existence of Hg–Hg atomic pairs have ever been demonstrated, and the HgII partitioning among the two protein domains is unknown. Using high energy‐resolution XANES spectroscopy, MP2 geometry optimization, and biochemical analysis, evidence for the coexistence of two‐coordinate Hg‐thiolate complex and four‐coordinate Hg‐thiolate cluster with a metacinnabar‐type (β‐HgS) structure in the α domain of separate metallothionein molecules from blue mussel under in vivo exposure is provided. The findings suggest that the CXXC claw setting of thiolate donors, which only exists in the α domain, acts as a nucleation center for the polynuclear complex and that the five CXC motifs from this domain serve as the cluster‐forming motifs. Oligomerization is driven by metallophilic Hg⋅⋅⋅Hg interactions. Our results provide clues as to why Hg has higher affinity for the α than the β domain. More generally, this work provides a foundation for understanding how metallothioneins mediate mercury detoxification in the cell under in vivo conditions.
Lewis Acid‐Mediated One‐Electron Reduction of Nitrous Oxide
Authors: Liu Yizhu , Solari Euro , Scopelliti Rosario , Fadaei Tirani Farzaneh , Severin Kay 
Published: November 2018

AbstractThe one‐electron reduction of nitrous oxide (N2O) was achieved using strong Lewis acids E(C6F5)3 (E=B or Al) in combination with metallocenes. In the case of B(C6F5)3, electron transfer to N2O required a powerful reducing agent such as Cp*2Co (Cp*=pentamethylcyclopentadienyl). In the presence of Al(C6F5)3, on the other hand, the reactions could be performed with weaker reducing agents such as Cp*2Fe or Cp2Fe (Cp=cyclopentadienyl). The Lewis acid‐mediated electron transfer from the metallocene to N2O resulted in cleavage of the N−O bond, generating N2 and the oxyl radical anion [OE(C6F5)3]⋅−. The latter is highly reactive and engages in C−H activation reactions. It was possible to trap the radical by addition of the Gomberg dimer, which acts as a source of the trityl radical.
Cyclische (Alkyl)(Amino) Carbene
Authors: Paul Ursula S. D. , Krahfuß Mirjam J. , Radius Udo 
Published: November 2018

ZusammenfassungMit den cyclischen (Alkyl)(amino)carbenen wurde die sehr wichtige Ligandenklasse der Carbene um einen neuen, vielseitig einsetzbaren Vertreter erweitert. Dank ihrer sterischen und elektronischen Eigenschaften eignen sich cAACs unter anderem als Liganden in der Übergangsmetallchemie z. B. zur Darstellung von Katalysatoren und zur Stabilisierung von Metallatomen in ungewöhnlichen Oxidationsstufen. In der Hauptgruppenchemie finden sie als reaktive Organokatalysatoren Anwendung zur Aktivierung kleiner Moleküle und enthalpisch starker Bindungen. In diesem Artikel werden einige Beispiele der aktuellen Forschung sowohl aus der Hauptgruppen‐ als auch aus der Übergangsmetallchemie diskutiert und im Zuge dessen einige grundlegende Konzepte der organischen und anorganischen Chemie vermittelt.
Free Radical Pathway Cleavage of C—O Bonds for the Synthesis of Alkylboron Compounds
Authors: Lu Xi , Zhang Zhen‐Qi , Yu Lu , Zhang Ben , Wang Bing , Gong Tian‐Jun , Tian Chang‐Lin , Xiao Bin , Fu Yao 
Published: November 2018

Summary of main observation and conclusionWe report a silver‐catalyzed borylation of alkyl tosylates, which provides a new method for the synthesis of alkylboron compounds with good functional group compatibility and excellent chemoselectivity. The present work added highly polarized alkyl tosylate C—O bonds to the fairly limited number of C—O bonds able to participate in free radical cleavage pathways. The mechanistic studies suggested that in situ‐generated silver(0) catalytic species were the active catalytic species and played a key role in the radical pathway cleavage of C—O bonds.
Does race predict the development of metastases in men who receive androgen‐deprivation therapy for a biochemical recurrence after radical prostatectomy?
Authors: Vidal Adriana C. , Howard Lauren E. , De Hoedt Amanda , Kane Christopher J. , Terris Martha K. , Aronson William J. , Cooperberg Matthew R. , Amling Christopher L. , Lechpammer Stanislav , Flanders Scott C. , Freedland Stephen J. 
Published: November 2018

BackgroundIn this study among men who underwent radical prostatectomy (RP), African American men (AAM) were 28% more likely to develop recurrent disease compared with Caucasian men (CM). However, among those who had nonmetastatic, castration‐resistant prostate cancer (CRPC), race did not predict metastases or overall survival. Whether race predicts metastases among men who receive androgen‐deprivation therapy (ADT) after a biochemical recurrence (BCR) (ie, before CRPC but after BCR) is untested.MethodsThe authors identified 595 AAM and CM who received ADT for a BCR that developed after RP between 1988 and 2015 in the Shared Equal‐Access Regional Cancer Hospital (SEARCH) database. Univariable and multivariable Cox models were used to test the association between race and the time from ADT to metastases. Secondary outcomes included the time to CRPC, all‐cause mortality, and prostate cancer‐specific mortality.ResultsDuring a median follow‐up of 66 months after ADT, 62 of 354 CM (18%) and 38 of 241 AAM (16%) developed metastases. AAM were younger at the time they received ADT (63 vs 67 years; P < .001), had received ADT in a more recent year (2008 vs 2006; P < .001), had higher prostate‐specific antigen levels at RP (11.1 vs 9.2 ng/mL; P < .001), lower pathologic Gleason scores (P = .004), and less extracapsular extension (38% vs 48%; P = .022). On multivariable analysis, there was no association between race and metastases (hazard radio, 1.20; P = .45) or any of the other secondary outcomes (all P > .5).ConclusionsAmong veterans who received ADT post‐BCR after RP, race was not a predictor of metastases or other adverse outcomes. The current findings suggest that research efforts to understand racial differences in prostate cancer biology should focus on early stages of the disease (ie, closer to the time of diagnosis).
A phase 2 trial of abiraterone acetate without glucocorticoids for men with metastatic castration‐resistant prostate cancer
Authors: McKay Rana R. , Werner Lillian , Jacobus Susanna J. , Jones Alexandra , Mostaghel Elahe A. , Marck Brett T. , Choudhury Atish D. , Pomerantz Mark M. , Sweeney Christopher J. , Slovin Susan F. , Morris Michael J. , Kantoff Philip W. , Taplin Mary‐Ellen 
Published: November 2018

AbstractBackgroundAbiraterone acetate suppresses adrenal androgens and glucocorticoids through the inhibition of CYP17; however, given the risk of mineralocorticoid excess, it is administered with glucocorticoids. Herein, the authors performed a phase 2, single‐arm study that was designed to assess the safety of abiraterone acetate without steroids in patients with castration‐resistant prostate cancer.MethodsEligible patients had castration‐resistant prostate cancer with controlled blood pressure and normal potassium. Patients initially received abiraterone acetate at a dose of 1000 mg daily alone. Those with persistent or severe mineralocorticoid toxicity received treatment with prednisone initiated at a dose of 5 mg twice daily. Therapy was continued until radiographic progression, toxicity, or withdrawal. The primary objective of the current study was to determine the percentage of men requiring prednisone to manage mineralocorticoid toxicity. Toxicity was graded according to Common Terminology Criteria for Adverse Events, version 4.0.ResultsA total of 58 patients received at least 1 dose of abiraterone acetate; the majority had metastases (53 patients; 91.4%). Sixteen patients (27.6%) received prior chemotherapy, 6 patients (10.3%) received prior enzalutamide, and 4 patients (7%) received prior ketoconazole. Grade 3 to 4 adverse events of interest included hypertension (9 patients; 15.5%) and hypokalemia (4 patients; 7%). There was no grade ≥3 edema. Seven patients (12%) initiated prednisone therapy for mineralocorticoid toxicity, 3 patients for hypertension (5%), and 4 patients for hypokalemia (7%). Two patients initiated prednisone therapy for fatigue (3%). Forty patients (68%) experienced a decline in prostate‐specific antigen of ≥50% with the use of abiraterone acetate alone. Patients with lower baseline levels of androstenedione (P = .04), androsterone (P = .01), dehydroepiandrosterone (P = .03), and 17‐hydroxyprogesterone (P = .03) were found to be more likely to develop mineralocorticoid toxicity.ConclusionsTreatment with abiraterone acetate without steroids is feasible, although clinically significant adverse events can occur in a minority of patients. The use of abiraterone acetate without prednisone should be balanced with the potential for toxicity and requires close monitoring.
ONOFIC‐based leakage reduction technique for FinFET domino circuits
Authors: Magraiya Vijay Kumar , Gupta Tarun Kumar 
Published: November 2018

SummaryA new technique ON/OFf logIC (ONOFIC) is proposed in this paper for designing domino logic circuits in fin‐field effect transistor (FinFET) deep submicron technology. In this technique, a block named ONOFIC is inserted between pull‐up network (PUN) and pull‐down network (PDN) of domino circuits. The proposed technique is simulated in FinFET short gate (SG) and low power (LP) mode. The subthreshold current which plays a major role to determinate leakage power is very low in this technique. Two‐, 4‐, 8‐, and 16‐input OR gates are simulated with 32‐nm node FinFET technology. In FinFET LP mode, the subthreshold leakage power of the proposed technique is reduced by 15% to 24.3% at 25°C and reduced by 8.71% to 23.4% at 110°C compared with standard domino circuits. The subthreshold leakage power of the proposed circuit is reduced by 19.2% to 57.3% at 25°C and reduced by 17.6% to 60.7% at 110°C compared with leakage control transistor (LECTOR)‐based circuits. In FinFET SG mode, the subthreshold leakage power of the proposed technique is reduced by 7.69% to 17.7% at 25°C and reduced by 0 to 7.85% at 110°C compared with standard domino circuits. The subthreshold leakage power of the proposed circuit is reduced by 60.4% to 73.9% at 25°C and reduced by 45.1% to 65.5% at 110°C compared with LECTOR‐based circuits. The proposed technique is also efficient to reduce subthreshold leakage power in deep nanometer technology nodes from 7 to 20 nm.
Estimates of gene flow and dispersal in wild riverine Brook Trout (Salvelinus fontinalis) populations reveal ongoing migration and introgression from stocked fish
Authors: Bruce Spencer A. , Wright Jeremy J. 
Published: November 2018

AbstractAs anthropogenic impacts accelerate changes to landscapes across the globe, understanding how genetic population structure is influenced by habitat features and dispersal is key to preserving evolutionary potential at the species level. Furthermore, knowledge of these interactions is essential to identifying potential constraints on local adaptation and for the development of effective management strategies. We examined these issues in Brook Trout (Salvelinus fontinalis) populations residing in the Upper Hudson River watershed of New York State by investigating the spatial genetic structure of over 350 fish collected from 14 different sampling locations encompassing three river systems. Population genetic analyses of microsatellite data suggest that fish in the area exhibit varying degrees of introgression from nearby State‐directed supplementation activities. Levels of introgression in these populations correlate with water‐way distance to stocking sites, although genetic population structure at the level of individual tributaries as well as their larger, parent river systems is also detectable and is dictated by migration and influenced by habitat connectivity. These findings represent a significant contribution to the current literature surrounding Brook Trout migration and dispersal, especially as it relates to larger interconnected systems. This work also suggests that stocking activities may have far‐reaching consequences that are not directly limited to the immediate area where stocking occurs. The framework and data presented here may aid in the development of other local aquatic species‐focused conservation plans that incorporate molecular tools to answer complex questions regarding diversity mapping, and genetically important conservation units.