bluuebunny/crossref_metadata_2025 huggingface dataset:
Ruddlesden–Popper Perovskites: Synthesis and Optical Properties for Optoelectronic Applications
Authors: Gao Xupeng , Zhang Xiangtong , Yin Wenxu , Wang Hua , Hu Yue , Zhang Qingbo , Shi Zhifeng , Colvin Vicki L. , Yu William W. , Zhang Yu
Published: October 2019

Ruddlesden–Popper perovskites with a formula of (A′)2(A)n−1BnX3n+1 have recently gained widespread interest as candidates for the next generation of optoelectronic devices. The variations of organic cation, metal halide, and the number of layers in the structure lead to the change of crystal structures and properties for different optoelectronic applications. Herein, the different synthetic methods for 2D perovskite crystals and thin films are summarized and compared. The optoelectronic properties and the charge transfer process in the devices are also delved, in particular, for light‐emitting diodes and solar cells.
Dispersion in steady and time‐oscillatory flows through an eccentric annulus
Authors: Chu Henry C. W. , Garoff Stephen , Tilton Robert D. , Khair Aditya S.
Published: October 2019

A multiple‐scale perturbation is conducted to derive an averaged equation for predicting the longtime solute transport in an eccentric annulus in which the uniaxial flow may oscillate periodically in time. A proof for the positiveness of the dispersivity is presented, implying that over a cycle of oscillation a solute cloud always broadens. For a steady flow driven by a fixed pressure gradient, increasing the eccentricity and annulus size gives rise to stronger dispersion. This relationship holds when the flow becomes unsteady. In the limit of slow oscillation, dispersion due to an oscillatory flow asymptotes to one‐half of that by a steady flow. Increasing the oscillation frequency leads to a two‐step decay of the dispersivity. The maximum dispersion in an oscillatory flow can be achieved in the limit of slow oscillation and large eccentricity, where dispersion can be O(103) times larger than that in an otherwise concentric annulus.
Turning the Tap: Conformational Control of Quantum Interference to Modulate Single‐Molecule Conductance
Authors: Jiang Feng , Trupp Douglas I. , Algethami Norah , Zheng Haining , He Wenxiang , Alqorashi Afaf , Zhu Chenxu , Tang Chun , Li Ruihao , Liu Junyang , Sadeghi Hatef , Shi Jia , Davidson Ross , Korb Marcus , Sobolev Alexandre N. , Naher Masnun , Sangtarash Sara , Low Paul J. , Hong Wenjing , Lambert Colin J.
Published: October 2019

Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum‐interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular‐design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) inmeta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular‐scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic‐ratio and orbital‐product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single‐molecule devices with desirable electronic functions.
Inversion externer asymmetrischer Induktion durch selektive Energietransfer‐Katalyse: Strategie zu β‐chiralen Phosphonat‐Antipoden
Authors: Onneken Carina , Bussmann Kathrin , Gilmour Ryan
Published: October 2019

Die enantiodivergente, katalytische Reduktion aktivierter Alkene überträgt stereochemische Informationen des chiralen Katalysators auf prochirale Substrate. Diese einflussreiche Strategie leidet häufig unter mangelnder Verfügbarkeit beider Katalysatorenantiomere. In dieser Studie wird die stereodivergente Hydrierung α,β‐ungesättigter Phosphonate mit nur einem einzelnen Enantiomer des Katalysators zur Herstellung von R‐ und S‐konfigurierten Phosphonaten mit entgegengesetzter Selektivität beschrieben. Dabei wird die Enantiodivergenz durch die Entwicklung einer einfachen E→Z‐Isomerisierung unter Verwendung von Anthracen als günstigem, organischem Photosensibilisator auf der Substratebene reguliert. Neben dem eigenen synthetischen Nutzen ermöglicht dieser Prozess eine darauffolgende stereospezifische, RhI‐katalysierte Hydrierung, mittels derer beide Produktenantiomere unter Verwendung des S‐Liganden hergestellt werden (bis zu 1:99 e.r.). Die Strategie übertrifft die mit dem E‐Substrat und R‐Liganden erhaltenen Selektivitäten.
Nucleation and Growth of Amino Acid and Peptide Supramolecular Polymers through Liquid–Liquid Phase Separation
Authors: Yuan Chengqian , Levin Aviad , Chen Wei , Xing Ruirui , Zou Qianli , Herling Therese W. , Challa Pavan Kumar , Knowles Tuomas P. J. , Yan Xuehai
Published: October 2019

The transition of peptides and proteins from the solution phase into fibrillar structures is a general phenomenon encountered in functional and aberrant biology and is increasingly exploited in soft materials science. However, the fundamental molecular events underpinning the early stages of their assembly and subsequent growth have remained challenging to elucidate. Here, we show that liquid–liquid phase separation into solute‐rich and solute‐poor phases is a fundamental step leading to the nucleation of supramolecular nanofibrils from molecular building blocks, including peptides and even amphiphilic amino acids. The solute‐rich liquid droplets act as nucleation sites, allowing the formation of thermodynamically favorable nanofibrils following Ostwald's step rule. The transition from solution to liquid droplets is entropy driven while the transition from liquid droplets to nanofibrils is mediated by enthalpic interactions and characterized by structural reorganization. These findings shed light on how the nucleation barrier toward the formation of solid phases can be lowered through a kinetic mechanism which proceeds through a metastable liquid phase.
Inverting External Asymmetric Induction via Selective Energy Transfer Catalysis: A Strategy to β‐Chiral Phosphonate Antipodes
Authors: Onneken Carina , Bussmann Kathrin , Gilmour Ryan
Published: October 2019

Enantiodivergent, catalytic reduction of activated alkenes relays stereochemical information encoded in the antipodal chiral catalysts to the pro‐chiral substrate. Although powerful, the strategy remains vulnerable to costs and availability of sourcing both catalyst enantiomers. Herein, a stereodivergent hydrogenation of α,β‐unsaturated phosphonates is disclosed using a single enantiomer of the catalyst. This enables generation of the R‐ or S‐configured β‐chiral phosphonate with equal and opposite selectivity. Enantiodivergence is regulated at the substrate level through the development of a facile E → Z isomerisation. This has been enabled for the first time by selective energy transfer catalysis using anthracene as an inexpensive organic photosensitiser. Synthetically valuable in its own right, this process enables subsequent RhI‐mediated stereospecific hydrogenation to generate both enantiomers of the product using only the S‐catalyst (up to 99:1 and 3:97 e.r.). This strategy out‐competes the selectivities observed with the E‐substrate and the R‐catalyst.
Freeing the Polarons to Facilitate Charge Transport in BiVO4 from Oxygen Vacancies with an Oxidative 2D Precursor
Authors: Qiu Weitao , Xiao Shuang , Ke Jingwen , Wang Zheng , Tang Songtao , Zhang Kai , Qian Wei , Huang Yongchao , Huang Duan , Tong Yexiang , Yang Shihe
Published: October 2019

The BiVO4 photoelectrochemical (PEC) electrode in tandem with a photovoltaic (PV) cell has shown great potential to become a compact and cost‐efficient device for solar hydrogen generation. However, the PEC part is still facing problems such as the poor charge transport efficiency owing to the drag of oxygen vacancy bound polarons. In the present work, to effectively suppress oxygen vacancy formation, a new route has been developed to synthesize BiVO4 photoanodes by using a highly oxidative two‐dimensional (2D) precursor, bismuth oxyiodate (BiOIO3), as an internal oxidant. With the reduced defects, namely the oxygen vacancies, the bound polarons were released, enabling a fast charge transport inside BiVO4 and doubling the performance in tandem devices based on the oxygen vacancy eliminated BiVO4. This work is a new avenue for elaborately designing the precursor and breaking the limitation of charge transport for highly efficient PEC‐PV solar fuel devices.
Transcriptome analysis of two radiated Cycas species and the subsequent species delimitation of the Cycas taiwaniana complex
Authors: Wang Xin‐Hui , Wu Wei , Jian Shu‐Guang
Published: October 2019

Premise

Cycas is an important gymnosperm genus, and the most diverse of all cycad genera. The C. taiwaniana complex of species are morphologically similar and difficult to distinguish due to a lack of genomic resources.

Methods

We characterized the transcriptomes of two closely related and endangered Cycas species endemic to Hainan, China: C. hainanensis and C. changjiangensis. Three single‐copy nuclear genes in the C. taiwaniana complex were sequenced based on these transcriptomes, enabling us to evaluate the species boundaries using the multispecies coalescent method implemented in the Bayesian Phylogenetics and Phylogeography program.

Results

We obtained 68,184 and 81,561 unigenes for C. changjiangensis and C. hainanensis, respectively. We identified six positively selected genes that are mainly involved in stimulus responses, suggesting that environmental adaptation may have played an important role in the relatively recent divergence of these species. The similar KS distribution peaks at 1.0 observed for the paralogs in the two species indicate a common whole‐genome duplication event. Our species delimitation analysis indicated that the C. taiwaniana complex consists of three distinct species, which correspond to the previously reported morphological differences.

Discussion

Our study provides valuable genetic resources for Cycas species and guidance for the taxonomic treatment of the C. taiwaniana complex, as well as new insights into evolution of species within Cycas.
Revealing Complex Ecological Dynamics via Symbolic Regression
Authors: Chen Yize , Angulo Marco Tulio , Liu Yang‐Yu
Published: October 2019

Understanding the dynamics of complex ecosystems is a necessary step to maintain and control them. Yet, reverse‐engineering ecological dynamics remains challenging largely due to the very broad class of dynamics that ecosystems may take. Here, this challenge is tackled through symbolic regression, a machine learning method that automatically reverse‐engineers both the model structure and parameters from temporal data. How combining symbolic regression with a “dictionary” of possible ecological functional responses opens the door to correctly reverse‐engineering ecosystem dynamics, even in the case of poorly informative data, is shown. This strategy is validated using both synthetic and experimental data, and it is found that this strategy is promising for the systematic modeling of complex ecological systems.
Supratentorial infarcts accompanying hiccup
Authors: Itabashi Ryo , Endo Kaoru , Saito Takuya , Fukuma Kazuki , Yazawa Yukako
Published: October 2019

Backgrounds

The main culprit lesion causing hiccup in patients with ischemic stroke is thought to involve the medulla oblongata, but some cases of hiccups caused by damage to the supratentorial cortex have been reported. The present study aimed to address the clinical and radiological characteristics of acute stroke patients accompanied by hiccups caused by supratentorial lesions.

Method

We retrospectively studied 5,309 consecutive patients with acute ischemic stroke or transient ischemic attack who were admitted to our institute within 7 days after onset between April 2006 and September 2017. We searched for the term “hiccup” in prospectively collected descriptive datasets and analyzed associations between hiccup and clinical and radiological findings, with particular focus on patients with supratentorial lesions.

Results

We finally selected 16 stroke patients accompanied by hiccup. Nine patients had infarcts in the lateral medulla oblongata, and others had supratentorial infarcts (three patients with cortical infarcts, four patients with subcortical infarcts). Moreover, the right hemisphere was frequently damaged in this series (6/7, 86%).

Conclusions

Hiccup could be caused by supratentorial infarcts including the insular cortex, temporal lobe, and subcortex.
Green supply chain management: Pressures, practices, and performance—An integrative literature review
Authors: Balon Virendra
Published: October 2019

The evolution of supply chain management, such as green supply chain and sustainable supply chain implementation in the industry, has been a great momentum over the past two decades, particularly from the mid of third industrial revolution to the current fourth industrial revolution. Given this interest, engineering and management scholars have examined various concepts and theoretical developments of green supply chain management (GSCM), especially during the past decade. The purpose of this paper, therefore, is to critically review the extant literature on pressures, practices, and performance of GSCM. The paper surveyed more than 150 research articles published in high‐impact refereed academic journals. The review synthesis has been discussed through GSCM pressures (government rules and regulations, corporate social responsibility, investment recovery, and green market), GSCM practices (eco‐design, internal environmental management, waste management, green purchasing aspect, quality, and product recovery), and GSCM performance (financial, operational, and environmental). Bibliometric results were presented, including the types of sources, year‐wise publications, country‐wise output, journal‐wise output, and top contributors in GSCM research.
Upregulation of nuclear‐enriched abundant transcript 1 confers oxaliplatin resistance to gastric cancer
Authors: Li Yunsong , Peng Chunwei , Fang Changyi , Huang Kai
Published: October 2019

The present study aims to investigate the roles of nuclear‐enriched abundant transcript 1 (NEAT1) in the regulation of oxaliplatin resistance to gastric cancer (GC). Oxaliplatin‐resistant cell lines were constructed using stepwise selection. NEAT1 knockdown and overexpression of NEAT1 were performed. The 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide (MTT) and colony formation assays were used to evaluate cell proliferation. Propidium iodide (PI) and annexin V staining were used to evaluate cell apoptosis. A dual‐luciferase reporter assay was used to evaluate the molecular interactions. Quantitative polymerase chain reaction (qPCR) was used to determine messenger RNA (mRNA) expression. Western blotting was used to determine the protein expression. Kaplan–Meier's analysis was performed to evaluate the relationship between NEAT1 and poor prognosis in GC. NEAT1 was upregulated in oxaliplatin‐resistant GC cells and associated with poor prognosis in GC patients. NEAT1 knockdown suppressed oxaliplatin resistance, whereas overexpression of NEAT1 induced oxaliplatin resistance. In addition, the expressions of NEAT1 were negatively associated with miR‐26 expressions. Overexpression of NEAT1 attenuated the inhibitory effects of miR‐26 on the enhancer of zeste homolog 2 (EZH2). The roles of NEAT1 in the regulation of oxaliplatin resistance to GC are in part by ameliorating the inhibitory effect of miR‐26 on EZH2.
Humidity—A Powerful Tool to Customize the Physical Properties of Molecular Magnets
Authors: Stefańczyk Olaf , Ohkoshi Shin‐ichi
Published: October 2019

Since the dawn of the century, people have been fascinated by the mysterious force that draws two pieces of lodestone (magnetite, Fe3O4) to each other as well as by property of stilbite (natural zeolite, NaCa4[Si27Al9O72]⋅28 H2O) to generate huge amounts of steam by rapidly heating the material. Nowadays, we know the first effect is addressed by magnetic attraction whereas the second one is related to the reversible sorption/desorption of water from humid air inside porous materials. For a long time, it was thought that these two, at first glance, were disjunctive properties that cannot be combined into one material. Nevertheless, the scientists have once again proved that there are no impossible things. Based on the discovery of the first molecular magnets, the idea to combine magnetic properties with other functionalities such as porosity gained great consideration by scientists from different research fields. Very soon, we witnessed numerous reports of novel multifunctional materials among which we can distinguish humidity‐responsive magnets. In this manuscript, the most outstanding results for such systems working at normal temperature and pressure (NTP) will be presented to motivate in‐depth research on this topic.
Mechanistic Study of the Solvent‐Dependent Formation of Extended and Stacked Supramolecular Polymers Composed of Bis(imidazolylporphyrinatozinc) Molecules
Authors: Satake Akiharu , Suzuki Yuki , Sugimoto Motonobu , Kuramochi Yusuke
Published: October 2019

Bis(imidazolylporphyrinatozinc) molecules linked through a 1,3‐butadiynylene moiety respond to the solvents they are dissolved in to afford exclusively extended (E) or stacked (S) supramolecular polymers. This system is expected to be a solvation/desolvation indicator. However, the principles underlying the solvent‐dependent formation of the two types of polymers and the mechanism of the transformation between them are unclear. The formation of the polymers is considered to depend on the two types of complementary coordination bonds that can be formed and the π–π interactions between the porphyrins. In this study, the contributions and solvent dependence of both the coordination bonds and the π–π interactions have been investigated. The results clearly indicate that the coordination bonds are weakly or little solvent‐dependent, and that the π–π interactions function effectively only in the inner porphyrins of the S‐polymer and are strongly solvent‐dependent. Thermodynamic analysis revealed that the formation of the E‐ or S‐polymer in solution is determined by the total energies and the type of solvent used. The transformation of the E‐ to S‐polymer was investigated by gel permeation chromatography. The kinetics of the transformation were also determined. The role of the terminal imidazolylporphyrinatozinc moieties was also investigated: The results indicate that the transformation from the E‐ to S‐polymer occurs by an exchange mechanism between the polymers, induced by attack of terminal free imidazolyl groups on a polymer to zinc porphyrins on other polymers.
A Photoactivatable Small‐Molecule Probe for the In Vivo Capture of Polyketide Intermediates
Authors: Kilgour Samantha L. , Jenkins Robert , Tosin Manuela
Published: October 2019

A photolabile carba(dethia) malonyl N‐acetylcysteamine derivative was devised and prepared for the trapping of biosynthetic polyketide intermediates following light activation. From the lasalocid A polyketide assembly in a mutant strain of the soil bacterium Streptomyces lasaliensis, a previously undetected cyclised intermediate was identified and characterised, providing a new outlook on the timing of substrate processing.
A General Strategy for Through‐Bond Energy Transfer Fluorescence Probes Combining Intramolecular Charge Transfer: A Silyl Ether System for Endogenous Peroxynitrite Sensing
Authors: Lu Gonghao , Guo Yuxin , Zhuo Jiezhen , Li Xue , Chi Haijun , Zhang Zhiqiang
Published: October 2019

A general strategy is reported for developing through‐bond energy transfer (TBET) fluorescence probes by combining intramolecular charge transfer (ICT). The strategy uses a coplanar donor‐π‐bridge‐acceptor system (SiOPh‐PyOH) without spirolactam. The off‐on switch of TBET and ICT is controlled by coplanar structure changes in the sensing process instead of spirolactam ring‐opening in traditional TBET probes. DFT calculations showed that the energy and charge transfers from SiOPh to PyOH are prohibited. Since the SiOPh has no fluorescence, the probe SiOPh‐PyOH shows fluorescence properties similar to that of pyrene. After sensing ONOO−, the silyl ether is removed and the probe changes into −OPh‐PyO−. Electron‐donating ICT from −OPh to PyO− induces a large redshift of emission to 594 nm (179 nm shift). TBET from −OPh to PyO− ensures the probe exhibits a large pseudo‐Stokes shift of 213 nm. Furthermore, the probe was successfully used in endogenous ONOO− detection. This study offers a new strategy for the construction of TBET probes emitting in the red region without spirolactam ring‐opening, a new ONOO− sensing system using silyl ether as a reaction site, and a method for the deprotection of silyl ethers with ONOOH under mild conditions.
Lead(II) Siloxides
Authors: Someşan Adrian‐Alexandru , Le Coz Erwann , Raţ Ciprian Ionuţ , Dorcet Vincent , Roisnel Thierry , Silvestru Cristian , Sarazin Yann
Published: October 2019

Although PbII‐siloxides have been known until now to decompose to oxoclusters, here [{ROF}PbOSi(SiMe3)3] (ROF=fluoroalkoxide) and, most importantly, [Pb2{OSi(SiMe3)3}{μ2‐OSi(SiMe3)3}3], are presented. The unusual bonding pattern in the latter thermally stable dinuclear complex was investigated by crystallographic and computational methods. Its stability is much higher than that of the simple, yet elusive “[Pb(OSiPh3)2]”, for which decomposition pathways towards [Pb4(μ4‐O)(μ2‐OSiPh3)6] have been clearly established.
Fine Bubble‐based CO2 Capture Mediated by Triethanolamine Coupled to Whole Cell Biotransformation
Authors: Ohde Daniel , Thomas Benjamin , Matthes Simon , Percin Zeynep , Engelmann Claudia , Bubenheim Paul , Terasaka Koichi , Schlüter Michael , Liese Andreas
Published: October 2019

Carbon capture technology can be set up in combination with biocatalysis to utilize the bound CO2 as substrate in the Kolbe‐Schmitt like enzymatic reaction. The exemplary whole cell biotransformation of catechol to 2,3‐dihydroxybenzoic acid in a triethanolamine‐mediated multiphase system shows increased equilibrium conversion. Apart from the beneficial thermodynamics, the inherent fluid properties of triethanolamine is enabling easy application of CO2 fine bubbles as highly efficient gassing method to minimize the CO2 demand and CO2 emissions.
Rationalising Supramolecular Hydrogelation of Bis‐Urea‐Based Gelators through a Multiscale Approach
Authors: Van Lommel Ruben , Rutgeerts Laurens A. J. , De Borggraeve Wim M. , De Proft Frank , Alonso Mercedes
Published: October 2019

The current approach to designing low‐molecular‐weight gelators relies on a laborious trial‐and‐error process, mainly because of the lack of an accurate description of the noncovalent interactions crucial for supramolecular gelation. In this work, we report a multiscale bottom‐up approach composed of several computational techniques to unravel the key interactions in a library of synthesized bis‐urea‐based gelators and rationalize their experimentally observed hydrogelation performance. In addition to density functional theory calculations and molecular dynamics, the noncovalent interaction index is applied as a tool to visualise and identify the different types of noncovalent interactions. Interestingly, as well as hydrogen bonds between urea moieties, hydrogen bonds between a urea moiety and a pyridine ring were shown to play a detrimental role in the early aggregation phase. These findings enabled us to explain the hydrogelation performance observed in a library of twelve bis‐urea derivatives, which were synthesized with 58–95 % yields. From this library, three compounds were discovered to effectively gel water, with the most efficient hydrogelator only requiring a concentration of 0.2 w/v%.
Optimizing Tissue Preservation for High‐Resolution Confocal Imaging of Single‐Molecule RNA‐FISH
Authors: Redmayne Nash , Chavez Shawn L.
Published: October 2019

Over the past century, formalin‐fixed, paraffin‐embedded (FFPE) tissue samples have represented the standard for basic histology and immunostaining. However, FFPE has several limitations and less stringent tissue preservation methods are required for the visualization of nucleic acids at high resolution, particularly those that are expressed at low levels. Here, we describe the FFPE properties that negatively impact RNA integrity, an alternative tissue preservation technique that prevents RNA loss, and the steps necessary to optimize slide preparation for single‐molecule RNA fluorescent in situ hybridization (smRNA‐FISH) and imaging by confocal microscopy. This strategy retains RNA quality and eliminates formalin‐induced artifacts, thereby producing high‐resolution, diffraction‐limited confocal images of even rare RNA transcripts in tissues. As non‐coding RNAs and alternative splicing of gene isoforms continue to emerge as important regulators of human health and disease, a reliable, cost‐effective approach is required to examine the expression and localization of RNA targets in patient samples. © 2019 by John Wiley & Sons, Inc.

Basic Protocol 1: Preparing an RNase‐free workstation

Support Protocol 1: Diethyl pyrocarbonate water treatment

Support Protocol 2: Removing RNase contamination from glassware

Basic Protocol 2: BE70 tissue fixation and processing

Basic Protocol 3: Cutting slide sections from paraffin blocks

Basic Protocol 4: Specimen pre‐treatment

Basic Protocol 5: RNA fluorescent in situ hybridization labeling

Basic Protocol 6: Slide mounting

Basic Protocol 7: Generating deconvolution‐capable confocal micrographs
Electronic Health Record–Embedded Decision Support Platform for Morphine Precision Dosing in Neonates
Authors: Vinks Alexander A. , Punt Nieko C. , Menke Frank , Kirkendall Eric , Butler Dawn , Duggan Thomas J. , Cortezzo DonnaMaria E. , Kiger Sam , Dietrich Tom , Spencer Paul , Keefer Rob , Setchell Kenneth D.R. , Zhao Junfang , Euteneuer Joshua C. , Mizuno Tomoyuki , Dufendach Kevin R.
Published: October 2019

Morphine is the opioid most commonly used for neonatal pain management. In intravenous form, it is administered as continuous infusions and intermittent injections, mostly based on empirically established protocols. Inadequate pain control in neonates can cause long‐term adverse consequences; however, providing appropriate individualized morphine dosing is particularly challenging due to the interplay of rapid natural physiological changes and multiple life‐sustaining procedures in patients who cannot describe their symptoms. At most institutions, morphine dosing in neonates is largely carried out as an iterative process using a wide range of starting doses and then titrating to effect based on clinical response and side effects using pain scores and levels of sedation. Our background data show that neonates exhibit large variability in morphine clearance resulting in a wide range of exposures, which are poorly predicted by dose alone. Here, we describe the development and implementation of an electronic health record–integrated, model‐informed decision support platform for the precision dosing of morphine in the management of neonatal pain. The platform supports pharmacokinetic model‐informed dosing guidance and has functionality to incorporate real‐time drug concentration information. The feedback is inserted directly into prescribers' workflows so that they can make data‐informed decisions. The expected outcomes are better clinical efficacy and safety with fewer side effects in the neonatal population.
Going beyond defining: Preschool educators' use of knowledge in their pedagogical reasoning about vocabulary instruction
Authors: Dwyer Julie , Schachter Rachel E.
Published: October 2019

Previous research investigating both the knowledge of early childhood educators and the support for vocabulary development present in early childhood settings has indicated that both educator knowledge and enacted practice are less than optimal, which has grave implications for children's early vocabulary learning and later reading achievement. Further, the nature of the relationship between educators' knowledge and practice is unclear, making it difficult to discern the best path towards improved knowledge, practice, and children's vocabulary outcomes. The purpose of the present study was to add to the existing literature by using stimulated recall interviews and a grounded approach to examine how 10 preschool educators used their knowledge to made decisions about their moment‐to‐moment instruction in support of children's vocabulary development. Results indicate that educators were thinking in highly context‐specific ways about their goals and strategies for supporting vocabulary learning, taking into account important knowledge of their instructional history with children and of the children themselves to inform their decision making in the moment. In addition, they reported thinking about research‐based goals and strategies for supporting vocabulary learning that went beyond simply defining words for children. Implications for research and professional development are discussed.
Factors influencing plasticity in the arrival‐breeding interval in a migratory species reacting to climate change
Authors: Low Matthew , Arlt Debora , Knape Jonas , Pärt Tomas , Öberg Meit
Published: October 2019

Climate change is profoundly affecting the phenology of many species. In migratory birds, there is evidence for advances in their arrival time at the breeding ground and their timing of breeding, yet empirical studies examining the interdependence between arrival and breeding time are lacking. Hence, evidence is scarce regarding how breeding time may be adjusted via the arrival‐breeding interval to help local populations adapt to local conditions or climate change. We used long‐term data from an intensively monitored population of the northern wheatear (Oenanthe oenanthe) to examine the factors related to the length of 734 separate arrival‐to‐breeding events from 549 individual females. From 1993 to 2017, the mean arrival and egg‐laying dates advanced by approximately the same amount (~5–6 days), with considerable between‐individual variation in the arrival‐breeding interval. The arrival‐breeding interval was shorter for: (a) individuals that arrived later in the season compared to early‐arriving birds, (b) for experienced females compared to first‐year breeders, (c) as spring progressed, and (d) in later years compared to earlier ones. The influence of these factors was much larger for birds arriving earlier in the season compared to later arriving birds, with most effects on variation in the arrival‐breeding interval being absent in late‐arriving birds. Thus, in this population it appears that the timing of breeding is not constrained by arrival for early‐ to midarriving birds, but instead is dependent on local conditions after arrival. For late‐arriving birds, however, the timing of breeding appears to be influenced by arrival constraints. Hence, impacts of climate change on arrival dates and local conditions are expected to vary for different parts of the population, with potential negative impacts associated with these factors likely to differ for early‐ versus late‐arriving birds.
Grandmothers and deadly snakes: an unusual project in “citizen science”
Authors: Goiran Claire , Shine Richard
Published: October 2019

We describe initial results of an innovative citizen science project that is unusual in its taxonomic focus (deadly sea snakes), its location (the Indo‐Pacific), and its primary contributors (grandmothers from the city of Noumea, New Caledonia).
Tf2O‐Mediated Intermolecular Coupling of Secondary Amides with Enamines or Ketones: A Versatile and Direct Access to β‐Enaminones
Authors: Liu Yong‐Peng , Zhu Cheng‐Jie , Yu Cun‐Cun , Wang Ai‐E , Huang Pei‐Qiang
Published: October 2019

Based on the Tf2O‐mediated intermolecular reaction of secondary amides with enamines derived from ketones, a novel approach to β‐enaminones has been developed. The reaction is widely functional group tolerant and highly chemoselective. In the presence of 4 Å molecular sieves, the method can be extended to the one‐pot condensation of secondary amides with ketones for NH β‐enaminones synthesis.
Macrolide Core Synthesis of Calysolin IX Using an Intramolecular Glycosylation Approach
Authors: Nawój Mirosław , Grobelny Artur , Mlynarski Jacek
Published: October 2019

The utility of intramolecular glycosylation for the synthesis of the 27‐membered macrocyclic ring is highlighted in this first total synthesis of the most complex resin glycoside isolated to date – Calysolin IX. Oligosaccharide‐containing macrolides core was effectively constructed by TfOH/NIS‐promoted intramolecular glycosylation of thioglycosyl donor. As the glycosidic bond must be created en route to target structure, we show that this unusual yet efficient approach can effectively reduce the number of steps in the total synthesis of complex natural macrolides. This attempt is documented as an efficient tool in the synthesis of gigantic macrolide rings thus proving their practical utility in the total synthesis of sugar‐containing targets.
Gas film heat transfer as enhancement strategy for phase change materials
Authors: Arias Francisco J. , De Las Heras Salvador
Published: October 2019

In this work, consideration is given to an alternative strategy for phase change materials (PCMs) heat transfer enhancement with particular reference to horizontal plates. In contrast with current approaches in which heat transfer enhancement is pursued either by adapted geometries or acting on the thermal conductivity coefficient of a given PCM, here the problem is tackled by preventing the formation and contact of the front of solidification at the wall of the vessel by the deliberate presence of a gas film between the wall and the PCM. Because the presence of such a film, the front of solidification only can attains a certain critical thickness before gravitationally sinks by its own weight and then eliminating the continuous growth of the solid layer with the consequent reduction of conductive heat transfer and power output of the system as the solidification takes place which translates into an enhanced and steady power during the entire solidification process. It is shown that because the critical thickness of the solidified layer before sinks is a few millimeters or less and then smaller than practical gas films, therefore the heat transfer is controlled by the thickness and the thermal conductivity of the film. Additional R&D is required in order to arrive at a reliable practical and safe design.
Association between increased theta cordance and early response to ECT in late‐life depression
Authors: Ward Michael J. , Karim Helmet T. , Jessen Zachary F. , Ghuman Avniel Singh , Richardson R. Mark , Reynolds Charles F. , Karp Jordan F.
Published: October 2019

Objectives

More than half of patients with major depression who do not respond to initial antidepressants become treatment resistant (TRD), and while electroconvulsive therapy (ECT) is effective, it involves anesthesia and other medical risks that are of concern in geriatric patients. Past studies have suggested that theta cordance (TC), a correlate of cerebral metabolism measured by electroencephalography, could guide treatment decisions related to patient selection and engagement of the therapeutic target.

Methods/Design

Eight patients with late‐life treatment resistant depression (LL‐TRD) underwent magnetoencephalography (MEG) at baseline and following seven sessions of ECT. We tested whether the mean and regional frontal cortex TC were able to differentiate early responders from nonresponders.

Results

Five patients whose depression severity decreased by >30% after seven sessions were considered early responders. We found no baseline differences in mean frontal TC between early responders compared with nonresponders, but early responders exhibited a significant increase in TC following ECT. Further, we found that compared with nonresponders, early responders exhibited a greater change in TC specifically within the right prefrontal cortex.

Conclusions

These results support the hypothesis that increases in frontal TC are associated with antidepressant response. We expand on previous findings by showing that this change is specific to the right prefrontal cortex. Validation of this neural marker could contribute to improved ECT outcomes, by informing early clinical decisions about the acute efficacy of this treatment.
Dose volume effects of re‐irradiation for locally recurrent nasopharyngeal carcinoma
Authors: Ng Wai‐Tong , Lee Michael CH , Fung Nelson TC , Wong Edwin CY , Cheung Alice KW , Chow James CH , Au Kwok‐Hung , Poon Darren MC , Lai Jessica WY , Chiang Chi‐Leung , Choi Horace CW , Chau Tin‐Ching , Lee Victor HF , Lee Anne WM
Published: October 2019

Background

This study analyzed the dose volume effects of re‐irradiation for locally recurrent nasopharyngeal carcinoma (NPC) and attempts to determine the optimal dose for the best survival.

Methods

Ninety‐one patients were studied. The local control, fatal complication, and overall survival were analyzed against the dose (in Equivalent Dose at 2 Gy/fractions) and recurrent gross tumor volume (GTV).

Results

The local control and fatal complication rate appear to increase with prescribed dose. The overall survival peaks at around 60 Gy10. Local control decreases significantly with increasing GTV (P < .001) while overall survival shows similar trend (P = .06). No correlation was observed between the fatal complication rate and GTV volume. The dose response of local control appears to be stronger for smaller tumors.

Conclusion

GTV volume plays a significant role in local control. A 60 Gy10 appears to be optimal for the best survival outcome; higher doses might be considered for small tumors.
Novel genetic variants in KIF16B and NEDD4L in the endosome‐related genes are associated with nonsmall cell lung cancer survival
Authors: Yang Sen , Tang Dongfang , Zhao Yu C. , Liu Hongliang , Luo Sheng , Stinchcombe Thomas E. , Glass Carolyn , Su Li , Shen Sipeng , Christiani David C. , Wang Qiming , Wei Qingyi
Published: October 2019

The endosome is a membrane‐bound organ inside most eukaryotic cells, playing an important role in adaptive immunity by delivering endocytosed antigens to both MHC class I and II pathways. Here, by analyzing genotyping data from two published genome‐wide association studies (GWASs), we evaluated associations between genetic variants in the endosome‐related gene‐set and survival of patients with nonsmall cell lung cancer (NSCLC). The discovery included 44,112 (3,478 genotyped and 40,634 imputed) single‐nucleotide polymorphisms (SNPs) in 220 genes in a singlelocus analysis for their associations with survival of 1,185 NSCLC patients from the Prostate, Lung, Colorectal and Ovarian (PLCO) Cancer Screening Trial. After validation of the 821 survival‐associated significant SNPs in additional 984 NSCLC patients from the Harvard Lung Cancer Susceptibility Study, 14 SNPs remained significant. The final multivariate stepwise Cox proportional hazards regression modeling of the PLCO dataset identified three potentially functional and independent SNPs (i.e., KIF16B rs1555195 C>T, NEDD4L rs11660748 A>G and rs73440898 A>G) with an adjusted hazards ratio (HR) of 0.86 (95% confidence interval [CI] = 0.79–0.94, p = 0.0007), 1.31 (1.16–1.47, p = 6.0 × 10−5) and 1.27 (1.12–1.44, p = 0.0001) for overall survival (OS), respectively. Combined analysis of the adverse genotypes of these three SNPs revealed a trend in the genotype‐survival association (ptrend < 0.0001 for OS and ptrend < 0.0001 for disease‐specific survival). Furthermore, the survival‐associated KIF16B rs1555195T allele was significantly associated with decreased mRNA expression levels of KIF16B in both lung tissues and blood cells. Therefore, genetic variants of the endosome‐related genes may be biomarker for NSCLC survival, possibly through modulating the expression of corresponding genes.
Fabrication of electrospun poly(lactic acid) nanoporous membrane loaded with niobium pentoxide nanoparticles as a potential scaffold for biomaterial applications
Authors: Marins Natália H. , Silva Ricardo M. , Ferrua Camila P. , Łukowiec Dariusz , Barbosa Ananda M. , Ribeiro Juliana S. , Nedel Fernanda , Zavareze Elessandra R. , Tański Tomasz , Carreño Neftalí L. V.
Published: October 2019

Tissue engineering aims to regenerate and restore damaged human organs and tissues using scaffolds that can mimic the native tissues. The requirement for modern and efficient biomaterials that are capable of accelerating the healing process has been considerably increased. In this work, a novel electrospun poly(lactic acid) (PLA) nanoporous membrane incorporated with niobium pentoxide nanoparticles (Nb2O5) for biomaterial applications was developed. Nb2O5 nanoparticles were obtained by microwave‐assisted hydrothermal synthesis, and different concentrations (0, 1, 3, and 5% wt/wt) were tested. Chemical, morphological, mechanical, and biological properties of membranes were evaluated. Cell viability results demonstrated that the membranes presented nontoxic effects. The incorporation of Nb2O5 improved cell proliferation without impairing the wettability, porosity, and mechanical properties of membranes. Membranes containing Nb2O5 nanoparticles presented biocompatible properties with suitable porosity, which facilitated cell attachment and proliferation while allowing diffusion of oxygen and nutrients. This study has demonstrated that Nb2O5 nanoparticle‐loaded electrospun PLA nanoporous membranes are potential candidates for drug delivery and wound dressing applications.
Kidney Disease Progression Does Not Decrease Intestinal Phosphorus Absorption in a Rat Model of Chronic Kidney Disease–Mineral Bone Disorder
Authors: Vorland Colby J , Biruete Annabel , Lachcik Pamela J , Srinivasan Shruthi , Chen Neal X , Moe Sharon M , Hill Gallant Kathleen M
Published: October 2019

The Cy/+ rat has been characterized as a progressive model of chronic kidney disease–mineral bone disorder (CKD-MBD). We aimed to determine the effect of kidney disease progression on intestinal phosphorus absorption and whole-body phosphorus balance in this model. A total of 48 Cy/+ (CKD) and 48 normal littermates (NL) rats were studied at two ages: 20 weeks and 30 weeks, to model progressive kidney function decline at approximately 50% and 20% of normal kidney function. Sodium-dependent and sodium-independent intestinal phosphorus absorption efficiency were measured by the in situ jejunal ligated loop method using 33P radioisotope. Our results show that CKD rats had slightly higher sodium-dependent phosphorus absorption compared to NL rats, and absorption decreased from 20 to 30 weeks. These results are in contrast to plasma 1,25OH2D, which was lower in CKD rats. Gene expression of the major intestinal phosphorus transporter, NaPi-2b, was not different between CKD and NL rats in the jejunum but was lower in CKD rats versus NL rats in the duodenum. Jejunal ligated loop phosphorus absorption results are consistent with percent net phosphorus absorption results obtained from metabolic balance: higher net percent phosphorus absorption values in CKD rats compared with NL, and lower values in 30-week-olds compared with 20-week-olds. Phosphorus balance was negative (below zero) in CKD rats, significantly lower in 30-week-old rats compared with 20-week-old rats, and lower in CKD rats compared with NL rats at both ages. These results demonstrate no reduction in intestinal phosphorus absorption with progression of CKD despite lower 1,25OH2D status when assessed by an in situ ligated loop test, which is in contrast to the majority of in vitro studies, and if confirmed in further studies, could challenge the physiological relevance of in vitro findings. © 2019 American Society for Bone and Mineral Research.
The Associations Between Seven Different Types of Physical Activity and the Incidence of Fracture at Seven Sites in Healthy Postmenopausal UK Women
Authors: Armstrong Miranda EG , Lacombe Jason , Wotton Clare J , Cairns Benjamin J , Green Jane , Floud Sarah , Beral Valerie , Reeves Gillian K ,   for the Million Women Study Collaborators
Published: October 2019

There is a paucity of information on associations between specific types of physical activity and fracture risk at different sites in otherwise healthy postmenopausal women. Therefore, we examined risk of fracture at seven different sites associated with seven different types of physical activity in the population-based prospective UK Million Women Study. A total of 371,279 postmenopausal women (mean age 59.8 years), rating their health as good or excellent and reporting participation in walking, cycling, gardening, doing housework, yoga, dance, and sports club activities, were followed for site-specific incident fracture through record linkage to national databases on day-case and overnight hospital admissions. Cox regression yielded adjusted relative risks (RRs) and, because of the large number of statistical tests done, 99% confidence intervals (CIs) for fracture at seven different sites in relation to seven different physical activities. During an average follow-up of 12 years, numbers with a first site-specific fracture were as follows: humerus (2341), forearm (1238), wrist (7358), hip (4354), femur (not neck) (617), lower leg (1184), and ankle (3629). For upper limb fractures there was significant heterogeneity across the seven activity types (test for heterogeneity p = 0.004), with gardening more than 1 hour/week associated with a lower risk (RR = 0.91; 99% CI, 0.86 to 0.96; p < 0.0001), whereas cycling more than 1 hour/week was associated with an increased risk (RR = 1.11; 99% CI, 1.00 to 1.23; p = 0.008). For fractures of the lower limb (including hip) there was no significant heterogeneity by type of activity, with significant approximately 5% to 15% reductions in risk associated with most activities, except cycling. For hip fractures, there was no significant heterogeneity by type of activity, but with significant 15% to 20% reductions in risk associated with walking for 1 hour/day and participating in yoga and sporting activities. Physical activity is a modifiable risk factor for fracture, but the effects differ between different types of activities and different fracture sites. © 2019 The Authors. Journal of Bone and Mineral Research published by American Society for Bone and Mineral Research.