bluuebunny/crossref_metadata_2025_split huggingface dataset:
Efficient and Layer‐Dependent Exciton Pumping across Atomically Thin Organic–Inorganic Type‐I Heterostructures
Authors: Zhang Linglong , Sharma Ankur , Zhu Yi , Zhang Yuhan , Wang Bowen , Dong Miheng , Nguyen Hieu T. , Wang Zhu , Wen Bo , Cao Yujie , Liu Boqing , Sun Xueqian , Yang Jiong , Li Ziyuan , Kar Arara , Shi Yi , Macdonald Daniel , Yu Zongfu , Wang Xinran , Lu Yuerui 
Published: August 2018

AbstractThe fundamental light–matter interactions in monolayer transition metal dichalcogenides might be significantly engineered by hybridization with their organic counterparts, enabling intriguing optoelectronic applications. Here, atomically thin organic–inorganic (O–I) heterostructures, comprising monolayer MoSe2 and mono‐/few‐layer single‐crystal pentacene samples, are fabricated. These heterostructures show type‐I band alignments, allowing efficient and layer‐dependent exciton pumping across the O–I interfaces. The interfacial exciton pumping has much higher efficiency (>86 times) than the photoexcitation process in MoSe2, although the pentacene layer has much lower optical absorption than MoSe2. This highly enhanced pumping efficiency is attributed to the high quantum yield in pentacene and the ultrafast energy transfer between the O–I interface. Furthermore, those organic counterparts significantly modulate the bindings of charged excitons in monolayer MoSe2 via their precise dielectric environment engineering. The results open new avenues for exploring fundamental phenomena and novel optoelectronic applications using atomically thin O–I heterostructures.
Stereodiversified Modular Synthesis of Non‐planar Five‐Membered Cyclic N‐Hydroxylamidines: Reactivity Study and Application to the Synthesis of Cyclic Amidines
Authors: Prieto‐Ramírez Mary Cruz , Fernández Israel , da Silva Ivan , González‐Platas Javier , de Armas Pedro , García‐Tellado Fernando 
Published: August 2018

AbstractA modular, stereodiversified and scalable synthesis of 5‐membered cyclic N‐hydroxylamidines endowed with three contiguous stereogenic centres is reported. The synthesis utilizes 2‐cyano‐3‐aryl‐4‐nitro‐alkynoates as key building blocks, which are provided by a novel 3‐component Knoevenagel ‐Michael addition manifold carried out as an aqueous emulsion (on water). The key building blocks are obtained as separable mixtures of two series of diastereomers: 2,3,4‐syn,syn and 2,3,4‐syn,anti. Both series were separately transformed into the corresponding 5‐membered 3,4,5‐trisubstituted N‐hydroxylamidines by a tandem hydrogenation cyclization reaction (stereodiversification phase). These N‐hydroxylamidines are functionalized at C3‐methinic position of the ring (alpha to the amidine function) by a robust and unprecedented N‐amidinoxyl radical‐mediated auto‐oxidation process (hydroxylation), or by a diastereoselective enamine‐based C−C bond forming manifold (creation of an all‐carbon quaternary centre). The outcome of the latter is biased by the relative disposition of substituents in the ring, affording C3‐quaternized 5‐membered cyclic N‐hydroxylamidines or 2,9‐diazabicyclo[4.3.0]non‐1‐en motives. Finally, the Ti(III)‐reduction of these quaternized N‐hydroxylamidines generates the corresponding amidines in excellent yields.magnified image
Copper(II) Acetate‐Catalyzed Synthesis of Phosphorylated Pyridines via Denitrogenative C−P Coupling between Pyridotriazoles and P(O)H Compounds
Authors: Shen Ruwei , Dong Chao , Yang Jianlin , Han Li‐Biao 
Published: August 2018

AbstractA new inexpensive copper‐catalyzed denitrogenative C−P coupling reaction of pyridotriazoles with P(O)H compounds has been developed. The reaction proceeds via a process of copper‐catalyzed P(O)−H insertion into the pyridyl carbene intermediates generated in situ from pyridotriazoles. This reaction provides a new and effective method for the synthesis of a variety of 2‐picolylphosphoryl compounds.magnified image
Modulating BET Bromodomain Inhibitor ZEN‐3694 and Enzalutamide Combination Dosing in a Metastatic Prostate Cancer Patient Using CURATE.AI, an Artificial Intelligence Platform
Authors: Pantuck Allan J. , Lee Dong‐Keun , Kee Theodore , Wang Peter , Lakhotia Sanjay , Silverman Michael H. , Mathis Colleen , Drakaki Alexandra , Belldegrun Arie S. , Ho Chih‐Ming , Ho Dean 
Published: August 2018

AbstractCombination chemotherapy is a cornerstone of cancer treatment. Optimizing its effectiveness requires dose‐ and time‐dependent regulation of drug synergy. In this report, CURATE.AI, an artificial intelligence platform, is used to prospectively guide the dosing of a bromodomain inhibitor (ZEN‐3694) and enzalutamide administered in combination to a patient with metastatic castration‐resistant prostate cancer to reduce serum prostate‐specific antigen (PSA) levels. CURATE.AI successfully identifies substantial ZEN‐3694 and enzalutamide dose adjustments, increasing both treatment efficacy and tolerance. CURATE.AI analysis also confirms that the patient's durable response is mediated by ZEN‐3694 inclusion in the regimen. Due to CURATE.AI‐enhanced efficacy and safety, the patient was able to continue with the combination regimen, resulting in a durable response and no disease progression based on CURATE.AI‐sustained control over PSA levels and reduced lesion size.
Gold‐Catalyzed Site‐Selective C−H Bond Functionalization with Diazo Compounds
Authors: Ma Ben , Liu Lu , Zhang Junliang 
Published: August 2018

AbstractC−H bond functionalization has been one of most important subject in chemistry. The carbene transfer reaction is one of the most straightforward and efficient approaches for site‐selective C−H bond functionalization in the presence of transition‐metals. Gold catalysts, which are different with the common‐used transition‐metals (such as Rh, Cu, Ru, Fe), displayed their unique catalytic activity in carbene transfer reactions, especially for C−H bond functionalization. In this focus review, we summarized recent progress of C−H bond functionalization via the decomposition of diazo compounds catalyzed by gold complexes. We also highlighted the specificity and provided the mechanistic rationale to understand these reactions.
Reevaluating cases of trait‐dependent diversification in primates
Authors: Scott Jeremiah E. 
Published: August 2018

AbstractObjectivesPrevious investigations have identified several ecological traits that may have shaped differences in species richness among primate clades by influencing speciation and extinction probabilities. In this study, I reevaluate these cases in light of concerns about high false‐positive rates of the methods used to detect trait‐dependent diversification.Materials and methodsData for six traits were taken from the literature: activity pattern, sociality, mating system, terrestriality, frugivory, and mutualistic interactions with angiosperms (i.e., seed dispersal and pollination). These traits were treated as binary variables and analyzed in a phylogenetic framework using likelihood‐based and nonparametric methods for estimating trait‐specific diversification rates.ResultsOf the traits analyzed here, only activity pattern was found by all methods to be correlated with diversification: diurnal primates diversify at higher rates than nocturnal primates. Solitary foragers have a lower rate of diversification than group‐living primates, but this link is driven by the association between solitariness and nocturnality.DiscussionThese results indicate that ecological traits have had a more limited influence on primate diversification than suggested by previous studies. The false positives detected here can be linked with heterogeneity in diversification caused by sources other than the focal traits. One of these sources is the very high rate of diversification in Cercopithecoidea found in previous investigations. Another is the correlation between activity patterns and diversification. The underlying causal mechanism for the contrast in diversification dynamics between diurnal and nocturnal primates is unclear, but this correlation highlights the important role of activity pattern in shaping primate evolutionary history.
Long bone diaphyseal shape follows different ontogenetic trajectories in captive and wild gorillas
Authors: Canington Stephanie L. , Sylvester Adam D. , Burgess M. Loring , Junno Juho‐Antti , Ruff Christopher B. 
Published: August 2018

AbstractObjectivesA number of studies have demonstrated the ontogenetic plasticity of long bone diaphyseal structure in response to mechanical loading. Captivity should affect mechanical loading of the limbs, but whether captive apes grow differently than wild apes has been debated. Here, we compare captive and wild juvenile and adult Gorilla to ascertain whether growth trajectories in cross‐sectional diaphyseal shape are similar in the two environments.Materials and methodsA sample of young juvenile (n = 4) and adult (n = 10) captive Gorilla gorilla gorilla specimens, with known life histories, were compared with age‐matched wild G.g. gorilla (n = 62) and G. beringei beringei (n = 75) in relative anteroposterior to mediolateral bending strength of the femur, tibia, and humerus. Cross sections were obtained using peripheral quantitative CT.ResultsCaptive and wild adult G.g. gorilla differed in bending strength ratios for all three bones, but these differences were not present in young juvenile G.g. gorilla. In comparisons across taxa, captive juvenile G.g. gorilla were more similar to wild G.g. gorilla than to G.b. beringei, while captive adult G.g. gorilla were more similar in shape to G.b. beringei in the hind limb.DiscussionCaptive and wild G. gorilla follow different ontogenetic trajectories in long bone diaphyseal shape, corresponding to environmental differences and subsequent modified locomotor behaviors. Differences related to phylogeny are most evident early in development.
Transhumance pastoralism of Roccapelago (Modena, Italy) early‐modern individuals: Inferences from Sr isotopes of hair strands
Authors: Lugli Federico , Cipriani Anna , Tavaglione Valentina , Traversari Mirko , Benazzi Stefano 
Published: August 2018

AbstractObjectivesIn this work, we use Sr isotopes to analyze human hair and determine short‐term movements of a contemporary human traveler and of early‐modern individuals from an archaeological site (Roccapelago, Modena, Italy, 16th–18th century).Materials and methodsAnalyses were performed using a Neptune MC–ICP–MS. We first set up and tested the procedure on scalp hair of a contemporary human, who spent some time between Brazil and Italy. We then analyzed the 87Sr/86Sr ratios of eight exceptionally well‐preserved archaeological hair specimens associated with human mummies from Roccapelago. Trace elements were analyzed by LA‐ICP‐MS on single‐hair specimens to check the preservation of the archaeological samples.ResultsThe strontium isotope composition of modern human hair varies from 0.7087 to 0.7093. The 87Sr/86Sr ratios of the Roccapelago hair strands range from 0.7082 to 0.7137, with an average of 0.7093 ± 0.0031 (2σ), revealing also intra‐individual differences in isotopic composition along the length of the hair shaft. Data were compared with local archaeological rodent bones and teeth and with published isotopic values of water and outcropping rocks. Trace element abundances of archaeological and modern human hair are similarly low in terms of Rare Earth Element (REE) and metal contents, in particular after HNO3 leaching.DiscussionThe variable modern human hair 87Sr/86Sr ratios show that high‐resolution hair sampling tracks the movements of this individual between the two continents. The Sr isotope composition of the mummy hair is consistent with sub‐annual human movements from Roccapelago to an area with different 87Sr/86Sr ratios. Historical sources indicate that individuals from Roccapelago travelled with their herds to Tuscany for transhumance pastoralism practices. The high radiogenic 87Sr/86Sr ratios (>0.71) found in some of the hair are possibly consistent with the Tuscan Magmatic Province and the Tuscan Metamorphic Complex isotope signature. To our knowledge, this is the first study in an archaeological context where the Sr isotope evidence of mobility is corroborated by historical documents.
Evidence of variability in carbohydrate consumption in prehistoric fisher‐hunter‐gatherers of Southeastern Brazil: Spatiotemporal trends of oral health markers
Authors: Pezo‐Lanfranco Luis 
Published: August 2018

AbstractObjectivesIn this study, we evaluate the role of plants in the diet of fisher‐hunter gatherers adapted to highly productive coastal environments. Oral health markers were used to track spatiotemporal variations (regional and diachronic) in the composition of carbohydrate in the diets of prehistoric shell mound builders (sambaqui) from the Southeast of Brazil. Our main objective is to test the supposed stability in the dietary habits of sambaqui populations and identify modulating effects of chronological, cultural, and/or ecological factors.MethodsEighteen oral health markers (divided into three categories: caries, periodontal disease, and dental wear) were applied in 233 individuals from 7 sambaquis (dated between 4800 and 1100 BP) from 5 geographic regions.ResultsOur results reveal variable oral health patterns among sites. Despite that, we found a number of common features, such as dental wear and associated pulp lesions. Some oral health patterns are compatible with cariogenic diets and high carbohydrate consumption.ConclusionsOur analyses suggest that plant resource management is plausible at some sites and support the emerging evidence that plant consumption among sambaqui populations was driven more by ecologic factors than chronological or cultural ones. A comprehensive record of oral health markers shows promise as a methodology to differentiate between otherwise extremely similar diets.
Taphonomic inferences about Middle Pleistocene hominins: The human cranium of Gruta da Aroeira (Portugal)
Authors: Sanz Montserrat , Sala Nohemi , Daura Joan , Pantoja‐Pérez Ana , Santos Elena , Zilhão João , Arsuaga Juan Luis 
Published: August 2018

AbstractObjectivesThe aim of this work is to describe the taphonomic signatures of the Aroeira 3 cranium, with a specific focus on cranial breakage, comparing the cranium with other Middle and Upper Pleistocene hominin fossils in order to approximate the cause of death and the biological agencies and geologic processes involved in the taphonomic record of this specimen. Aroeira‐3 was recovered from Acheulean layer X of Gruta da Aroeira (Portugal), dated to 390–436 ka.Materials and methodsTaphonomic analyses noted surface modifications employing standard methods. The cranial breakage pattern of Aroeira 3 was analyzed to assess the presence/absence of perimortem (fresh bone) and postmortem (dry bone) fractures and the possible causes of perimortem skull bone fractures.ResultsAroeira 3 presents substantial bone loss of the left supraorbital arch and the outer cranial table of the frontal squama. Most of the fractures present features consistent with postmortem injuries. The fracture to the posterior region of the parietal bone, however, displays features more usually present in perimortem bone fractures. No evidence of anthropogenic activity or of carnivore modification has been identified. None of the expected features of interpersonal conflict are observed. Finally, the bone loss in the frontal squama and the supraorbital arch could be attributed to different agencies, and a traumatic event cannot be totally ruled out as origin of the bone alteration.DiscussionCannibalism, secondary treatment of the corpse and accumulation induced by carnivores can all be discarded, making an accident the most plausible explanation for the cranial fracture.
Cross‐sectional study of a United Kingdom cohort of neonatal vein of galen malformation
Authors: Lecce Francesca , Robertson Fergus , Rennie Adam , Heuchan Anne‐Marie , Lister Paula , Bhate Sanjay , Bhattacharya Jo , Brew Stefan , Kanagarajah Lakshmi , Kuczynski Adam , Peters Mark J. , Ridout Deborah , Schmitt Anne , Toolis Claire , Vargha‐Khadem Faraneh , Ganesan Vijeya 
Published: August 2018

ObjectiveDescribe the course and outcomes in a UK national cohort of neonates with vein of Galen malformation identified before 28 days of life.MethodsNeonates with angiographically confirmed vein of Galen malformation presenting to 1 of 2 UK treatment centers (2006–2016) were included; those surviving were invited to participate in neurocognitive assessment. Results in each domain were dichotomized into “good” and “poor” categories. Cross‐sectional and angiographic brain imaging studies were systematically interrogated. Logistic regression was used to explore potential outcome predictors.ResultsOf 85 children with neonatal vein of Galen malformation, 51 had survived. Thirty‐four participated in neurocognitive assessment. Outcomes were approximately evenly split between “good” and “poor” categories across all domains, namely, neurological status, general cognition, neuromotor skills, adaptive behavior, and emotional and behavioral development. Important predictors of poor cognitive outcome were initial Bicêtre score ≤ 12 and presence of brain injury, specifically white matter injury, on initial imaging; in multivariate analysis, only Bicêtre score ≤ 12 remained significant.InterpretationDespite modern supportive and endovascular treatment, more than one‐third of unselected newborns with vein of Galen malformation did not survive. Outcome was good in around half of survivors. The importance of white matter injury suggests that abnormalities of venous as well as arterial circulation are important in the pathophysiology of brain injury. Ann Neurol 2018;84:547–555
Sharp and Tunable Crystal/Fano‐Type Resonances Enabled by Out‐of‐Plane Dipolar Coupling in Plasmonic Nanopatch Arrays
Authors: Taghinejad Mohammad , Taghinejad Hossein , Malak Sidney T. , Moradinejad Hesam , Woods Eric V. , Xu Zihao , Liu Yawei , Eftekhar Ali A. , Lian Tianquan , Tsukruk Vladimir V. , Adibi Ali 
Published: August 2018

AbstractTuning resonance lineshapes of plasmonic structures is essential to create customized media with compelling optical properties for optimized light–matter interactions. The diversity of available metals and the variety of design architectures provide a rich portfolio for statically controlling the resonance lineshape. However, dynamic tuning of resonance attributes (e.g., the resonance wavelength and linewidth) are yet to be more expanded, especially when a narrow resonance linewidth is on demand. Here, using a plasmonic nanopatch array, sharp plasmonic crystal (PC) resonances are demonstrated across a wide spectral range of 230 nm, with full‐width at half‐maximum of only ≈6 nm. The combination of angle‐resolved ellipsometry and full‐wave simulations shows that diffractive coupling of out‐of‐plane electric dipoles is the principal contributor in the formation of such sharp PC resonances. In addition, the designed nanopatch PC supports a plasmonic Fabry–Pérot‐like resonance that can be interfered with the PC resonance to generate complex Fano‐type lineshapes. The coexistence of tunable resonance features renders the designed structures as a rich platform for applications seeking enhanced light–matter interactions and optical signal processing.
Nicht‐dirigierte kreuz‐dehydrierende (Hetero)arylierung von Allyl‐C(sp3)‐H‐Bindungen mittels C‐H‐Aktivierung
Authors: Lerchen Andreas , Knecht Tobias , Koy Maximilian , Ernst Johannes B. , Bergander Klaus , Daniliuc Constantin G. , Glorius Frank 
Published: August 2018

AbstractWir berichten über eine selektive, nicht‐dirigierte und kreuz‐dehydrierende Kupplung von Allyl‐C(sp3)‐H‐Bindungen mit C(sp2)‐H‐Bindungen von Heteroarenen. Die entwickelte Methode nutzt einfache, reichlich vorkommende Ausgangsmaterialien an Olefinen sowie an Heteroaromaten und konnte zur Modifikation von Pharmazeutika in späten Synthesestufen angewendet werden. Weiterhin liefert das entdeckte System ausschließlich die allylischen C‐C‐Kupplungsprodukte, weshalb das Substitutionsmuster der Olefine für weitere Funktionalisierungen erhalten bleibt.
Enzymkaskadenreaktionen in der Biosynthese
Authors: Walsh Christopher T. , Moore Bradley S. 
Published: August 2018

AbstractEnzym‐vermittelte Kaskadenreaktionen sind weit verbreitet. Um einen Vergleich mit den mechanistischen Kategorisierungen der komplementären Kaskadenreaktionen in der organischen Synthese zu ermöglichen sowie um die gemeinsamen Grundlagen aufzuzeigen, erörtern wir hier vier Arten von Enzymkaskadenreaktionen: vermittelt durch nucleophile, elektrophile, pericyclische und radikalische Reaktionen. Zwei Subtypen von Enzymen, die radikalische Kaskaden erzeugen, befinden sich an den entgegengesetzten Enden der Abundanzskala von Sauerstoff: Eisen‐basierte Enzyme nutzen O2, um hochvalente Eisen‐Oxo‐Spezies zu erzeugen, die nichtaktivierte C‐H‐Bindungen in Substraten homolytisch spalten und Gerüstumlagerungen einleiten. Am anaeroben Ende spalten Enzyme reversibel S‐Adenosylmethionin (SAM) unter Bildung des 5′‐Desoxyadenosyl‐Radikals als starkes Oxidans, um die homolytische Spaltung von C‐H‐Bindungen in gebundenen Substraten auszulösen. Die letztgenannten Enzyme werden als Radikal‐SAM‐Enzyme bezeichnet. Die erstgenannten Enzyme kategorisieren wir als “verhinderte Oxygenasen”.
Enantioselective Intramolecular Nicholas Reaction Catalyzed by Chiral Phosphoric Acid: Enantioconvergent Synthesis of Seven‐Membered Cyclic Ethers from Racemic Diols
Authors: Ota Yusuke , Kondoh Azusa , Terada Masahiro 
Published: August 2018

AbstractAn enantioconvergent intramolecular Nicholas reaction of racemic diols was developed using BINOL‐ and SPINOL‐derived phosphoric acids as the chiral Brønsted acid catalyst. The developed reaction features an efficient approach to the synthesis of seven‐membered cyclic ethers in a highly enantioselective manner. Further derivatization of the enantioenriched cyclic ethers, initiated by the de‐complexation of the dicobalt species, afforded densely functionalized cyclic ethers having an unsaturated diester moiety without loss of enantiomeric excess.
Endohedral Functionalized Cage as a Tool to Create Frustrated Lewis Pairs
Authors: Yang Jian , Chatelet Bastien , Dufaud Véronique , Hérault Damien , Michaud‐Chevallier Sabine , Robert Vincent , Dutasta Jean‐Pierre , Martinez Alexandre 
Published: August 2018

AbstractA frustrated Lewis pair (FLP) system was obtained by confinement of the Lewis base partner, a Verkade's superbase, in a molecular cavity. Whereas the model superbase lacking cavity displayed no catalytic activity in Morita–Baylis–Hillman (MBH) reactions, when associated to titanium (IV) chloride, the encaged superbase turns out to be an efficient catalyst under the same conditions. The crucial role of the endohedral functionalized cage on catalytic performance was further demonstrated by the fact that model superbases with bulky substituents were much less efficient to produce active catalysts, as well as by inhibition and substrate selection experiments. 31P NMR spectroscopy and mass spectrometry experiments evidenced that no interaction between the Lewis acidic and basic partners occurred when the superbase was capped by a cycloveratrylene (CTV) unit, thus creating a true FLP active system.