bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Selective Dihydrosilylation of Internal Alkynes Enabled by Rare‐Earth Ate Complex
Authors: Chen Wufeng , Song Haibin , Li Jianfeng , Cui Chunming 
Published: December 2019

AbstractHydrosilylation of alkynes generally yield vinylsilanes, which are inert to the further hydrosilylation because of the steric effects. Reported here is the first successful dihydrosilylation of aryl‐ and silyl‐substituted internal alkynes enabled by a rare‐earth ate complex to yield geminal bis‐ and tris(silanes), respectively. The lanthanum bis(amido) ate complex supported by an ene‐diamido ligand proved to be the ideal catalyst for this unprecedented transformation, while the same series of yttrium and samarium alkyl and samarium bis(amido) ate complexes exhibited poor activity and selectivity, indicating significant effects of the ionic size and ate structure of the rare‐earth catalysts.
Retracted: Circular RNA ANKRD36 attends to lipopolysaccharide‐aroused MRC‐5 cell injury via regulating microRNA‐31‐3p
Authors: Guo Rui , Zhang Lijuan , Meng Jingjing 
Published: December 2019

AbstractBackgroundSome circular RNAs (circRNAs) are reported to attend to the pathogenesis of pneumonia. This study tested the impact of circRNA ankyrin repeat domain 36 (circANKRD36) on human embryonic lung fibroblast MRC‐5 cell injury irritated by lipopolysaccharide (LPS).MethodsAfter LPS irritation, viability, apoptosis, ROS, protein, and cytokines, along with circANKRD36 were tested by CCK‐8, Annexin V‐FITC, DCFH‐DA, and ELISA or Western blot. si‐circANKRD36 and microRNA‐31‐3p/5p (miR‐31‐3p/5p) inhibitor were applied to silence circANKRD36 and miR‐31‐3p/5p. miR‐31‐3p/5p mimic was utilized to upregulate miR‐31‐3p/5p. RT‐qPCR was used to detect miRNAs. The relationship between miRNAs and MyD88 or IL‐34 was analyzed by luciferase activity reporter assay.ResultsLPS aroused a decrease in viability, increases in apoptosis, ROS, and IL‐6, IL‐8, and TNF‐α, along with circANKRD36, and activation of NF‐κB pathway. Silencing circANKRD36 weakened the above‐mentioned influences of LPS. Moreover, silencing circANKRD36 hoisted miR‐31‐3p expression. Silencing miR‐31‐3p mitigated the impacts of circANKRD36 silence on LPS‐irritated MRC‐5 cells. Besides, MyD88 was a downstream target of miR‐31‐3p, and 3′UTR of IL‐34 mRNA was targeted by miR‐31‐5p. LPS induced the accumulation of MyD88. Silencing MyD88 was constructive to maintain cell viability, retard apoptosis and inhibit adverse oxidation and inflammation.ConclusionThis research verified that silencing circANKRD36 could weaken LPS‐irritated MRC‐5 cell injury via regulating miR‐31/MyD88‐mediated repression of NF‐κB pathway.
Effect of the concentration of protein and nanoparticles on the structure of biohybrid nanocomposites
Authors: Majorošová Jozefína , Schroer Martin A. , Tomašovičová Natália , Batková Marianna , Hu Po‐Sheng , Kubovčíková Martina , Svergun Dmitri I. , Kopčanský Peter 
Published: December 2019

AbstractWe present colloidal nanocomposites formed by incorporating magnetite Fe3O4 nanoparticles (MNPs) with lysozyme amyloid fibrils (LAFs). Preparation of two types of solutions, with and without addition of salt, was carried out to elucidate the structure of MNPs‐incorporated fibrillary nanocomposites and to study the effect of the presence of salt on the stability of the nanocomposites. The structural morphology of the LAFs and their interaction with MNPs were analyzed by atomic force microscopy and small‐angle x‐ray scattering measurements. The results indicate that conformational properties of the fibrils are dependent on the concentration of protein, and the precise ratio of the concentration of the protein and MNPs is crucially important for the stability of the fibrillary nanocomposites. Our results confirm that despite the change in fibrillary morphology induced by the varying concentration of the protein, the adsorption of MNPs on the surface of LAF is morphologically independent. Moreover, most importantly, the samples containing salt have excellent stability for up to 1 year of shelf‐life.
Effect of radiotherapy for rectal cancer on female sexual function: a prospective cohort study
Authors: Svanström Röjvall A , Buchli C , Bottai M , Ahlberg M , Flöter-Rådestad A , Martling A , Segelman J 
Published: December 2019

Abstract

Background
Clinical experience and limited data show that female sexual function is influenced negatively by preoperative radiotherapy (RT) for rectal cancer. The aim of this prospective study was to investigate the impact of RT on sexual function and ovarian reserve measured by levels of anti-Müllerian hormone (AMH).

Methods
Women with stage I–III rectal cancer scheduled for surgery with or without preoperative (chemo)RT were included and followed for 2 years. Female Sexual Function Index (FSFI) questionnaire responses and blood samples for hormone analyses, including AMH in women aged 45 years or less, were collected at baseline and during follow-up.

Results
In the group of 109 women who received preoperative RT, median scores in all FSFI domains decreased over time, as did the total FSFI score (from 18·5 (range 2·0–36·0) at baseline to 10·8 (2·0–34·8) at 2 years; P &lt; 0·001). In the group of 30 women who did not receive preoperative RT, only satisfaction declined over time (from 3·2 (0·8–6·0) to 1·8 (0·8–6·0); P = 0·012). In longitudinal regression analysis, the mean decline in FSFI total score was –9·33 (95 per cent c.i. –16·66 to –1·99; P = 0·013) for women who had preoperative RT compared with those who did not, with adjustment for age, Psychological General Well-being Index score and relationship with partner. A corresponding association was seen for arousal, lubrication, orgasm and pain. Five of six women aged 45 years or less with detectable serum levels of AMH at baseline had undetectable levels after RT.

Conclusion
Preoperative RT was associated with impairment in sexual function in women with rectal cancer. This needs to be considered when discussing choice of treatment and rehabilitation. In younger women, undetectable AMH levels after RT indicate an irreversible loss of ovarian follicles.
Integrated analysis of genomic and transcriptomic profiles identified a prognostic immunohistochemistry panel for esophageal squamous cell cancer
Authors: Yu Yue , Li Zhihua , Huang Chenjun , Fang Haisheng , Zhao Fei , Zhou Yue , Pan Xianglong , Li Qifan , Zhuang Yu , Chen Liang , Xu Jing , Wang Wei 
Published: December 2019

AbstractBackgroundThe poor outcome of patients with esophageal squamous cell carcinoma (ESCC) highlights the importance of the identification of novel effective prognostic biomarkers. We aimed to identify a clinically applicable prognostic immunohistochemistry (IHC) panel for ESCC.MethodsAn integrated analysis was performed to screen and establish a prognostic panel using exome sequencing profile from 81 pairs of ESCC samples and RNA expression microarray data from 119 ESCC subjects. Two independent ESCC cohorts were recruited as training and validation groups to test the prognostic value.ResultsThree genes were selected, namely, ANO1, GAL, and MMP3, which were aberrantly expressed in ESCC tumor tissues (P < .001). Among them, ANO1 and MMP3 were reserved for the construction of the prognostic panel due to their significant association with the prognosis of ESCC patients (P = .015 and P < .001). Patients with both ANO1+ and MMP3+ had a poorer prognosis than that with ANO1−/MMP3+, ANO1+/MMP3−, or ANO1−/MMP3 − in both the training set and validation set (P < .001). Receiver operating characteristic analysis showed that the combination of IHC panel and eighth American Joint Commission on Cancer staging yielded a better prognostic predictive efficacy compared with the two indexes alone (P < .001, area under curve: 0.752). Finally, a nomogram was created by integrating the IHC markers and clinicopathological risk factors to predict prognosis with a C‐index of 0.695 (95% confidence interval: 0.657‐0.734).ConclusionUsing an integrated multistage screening strategy, we identified and validated a valuable prognostic IHC panel for ESCC.
Reversed‐phase HPLC enantioseparation of pantoprazole using a teicoplanin aglycone stationary phase—Determination of the enantiomer elution order using HPLC‐CD analyses
Authors: Papp Lajos Attila , Foroughbakhshfasaei Mohammadhassan , Fiser Béla , Horváth Péter , Kiss Eszter , Sekkoum Khaled , Gyéresi Árpád , Hancu Gabriel , Noszál Béla , Szabó Zoltán‐István , Tóth Gergő 
Published: December 2019

AbstractA direct HPLC method was developed for the enantioseparation of pantoprazole using macrocyclic glycopeptide‐based chiral stationary phases, along with various methods to determine the elution order without isolation of the individual enantiomers. In the preliminary screening, four macrocyclic glycopeptide‐based chiral stationary phases containing vancomycin (Chirobiotic V), ristocetin A (Chirobiotic R), teicoplanin (Chirobiotic T), and teicoplanin‐aglycone (Chirobiotic TAG) were screened in polar organic and reversed‐phase mode. Best results were achieved by using Chirobiotic TAG column and a methanol‐water mixture as mobile phase. Further method optimization was performed using a face‐centered central composite design to achieve the highest chiral resolution. Optimized parameters, offering baseline separation (resolution = 1.91 ± 0.03) were as follows: Chirobiotic TAG stationary phase, thermostated at 10°C, mobile phase consisting of methanol/20mM ammonium acetate 60:40 v/v, and 0.6 mL/min flow rate. Enantiomer elution order was determined using HPLC hyphenated with circular dichroism (CD) spectroscopy detection. The online CD signals of the separated pantoprazole enantiomers at selected wavelengths were compared with the structurally analogous esomeprazole enantiomer. For further verification, the inline rapid, multiscan CD signals were compared with the quantum chemically calculated CD spectra. Furthermore, docking calculations were used to investigate the enantiorecognition at molecular level. The molecular docking shows that the R‐enantiomer binds stronger to the chiral selector than its antipode, which is in accordance with the determined elution order on the column—S‐ followed by the R‐isomer. Thus, combined methods, HPLC‐CD and theoretical calculations, are highly efficient in predicting the elution order of enantiomers.
PBCF‐Graphene: A 2D Sp2 Hybridized Honeycomb Carbon Allotrope with a Direct Band Gap
Authors: Zhang Wei , Chai Changchun , Fan Qingyang , Song Yanxing , Yang Yintang 
Published: December 2019

AbstractInspired by the synthesis of graphene with benzene as the precursor, a novel all‐sp2 hybridized two‐dimensional (2D) carbon allotrope is proposed in this work. This 2D carbon allotrope is a poly‐butadiene‐cyclooctatetraene‐framework and displays a P6/mmm space group with 24 carbon atoms in a hexagonal unit cell (denoted as PBCF‐graphene). First‐principles calculations show the presence of a honeycomb structure along the c‐axis that possesses two kinds of holes with diameters of 4.88 and 2.39 Å. PBCF‐graphene has a direct band gap of 1.355 eV at the Γ point as determined using the HSE06 hybrid functional. This structure is energetically preferable over E‐graphene, C33‐carbon sheets, cyclo[18]carbon and C20 fullerenes and is the same to PCF‐graphene. Its dynamical, thermal and mechanical stabilities are proven from the phonon dispersion, ab initio molecular dynamics (AIMD simulations and elastic constants, respectively. It can not only withstand equi‐biaxial tensile strains as high as 17.6% but can also withstand temperatures at least 1000 K. PBCF‐graphene exhibits a high, room temperature, in‐plane, electron mobility, which is higher than the electron mobility of monolayer black phosphorus and 5.9 times higher than the hole mobility of monolayer MoS2. In addition, PBCF‐graphene can absorb photons from the visible to near‐ultraviolet regimes, giving it potential value in applications for nanoelectronic and optoelectronic devices.
On the Interplay between Charge‐Shift Bonding and Halogen Bonding
Authors: Sarr Serigne , Graton Jérôme , Montavon Gilles , Pilmé Julien , Galland Nicolas 
Published: December 2019

AbstractThe nature of halogen‐bond interactions has been analysed from the perspective of the astatine element, which is potentially the strongest halogen‐bond donor. Relativistic quantum calculations on complexes formed between halide anions and a series of Y3C−X (Y=F to X, X=I, At) halogen‐bond donors disclosed unexpected trends, e. g., At3C−At revealing a weaker donating ability than I3C−I despite a stronger polarizability. All the observed peculiarities have their origin in a specific component of C−Y bonds: the charge‐shift bonding. Descriptors of the Quantum Chemical Topology show that the halogen‐bond strength can be quantitatively anticipated from the magnitude of charge‐shift bonding operating in Y3C−X. The charge‐shift mechanism weakens the ability of the halogen atom X to engage in halogen bonds. This outcome provides rationales for outlier halogen‐bond complexes, which are at variance with the consensus that the halogen‐bond strength scales with the polarizability of the halogen atom.
Piano Stool Aminoalkylidene‐Ferracyclopentenone Complexes from Bimetallic Precursors: Synthesis and Cytotoxicity Data
Authors: Rocco Dalila , Batchelor Lucinda K. , Ferretti Eleonora , Zacchini Stefano , Pampaloni Guido , Dyson Paul J. , Marchetti Fabio 
Published: December 2019

AbstractThe reaction of pyrrolidine with a series of cationic diiron cyclopentadienyl complexes containing a bridging vinyliminium ligand gives access to piano stool monoiron complexes based on a five‐membered metallacycle that includes a vinyl‐aminoalkylidene moiety, in moderate to high yields. The resulting metallacyclic motif (aminoalkylidene‐ferracyclopentenone) is unique in organometallic chemistry and is partially pre‐constructed on the dinuclear frame. The monoiron products were fully characterized by elemental analysis, IR and multinuclear NMR spectroscopy, and in a number of cases by X‐ray diffraction and cyclic voltammetry. They are robust in aqueous solutions and generally unreactive towards alkylating agents in organic solvents. However, a cationic derivative was prepared in high yield by methylation of a 2‐pyridyl group. The cytotoxicity of both neutral and ionic complexes was assessed on cancerous (A2780 and A280cisR) and non‐cancerous (HEK293) cell lines, revealing the influence of local structural modifications on the antiproliferative activity and the selectivity of the compounds.
Structural and Non‐Covalent Interactions Study of 2‐Pyridone Based Flexible Unsymmetrical Dimer
Authors: Singh Ved P. , Dowarah Jayanta , Lalhruaizela  , Geiger David K. 
Published: December 2019

AbstractNon‐covalent weak interactions play a vital role in the stabilization of solid‐state structures. This manuscript describes the X‐ray crystallographic study of 4,6‐dimethyl‐2‐oxo‐1‐(3‐(p‐tolyloxy)propyl)‐1,2‐dihydropyridine‐3‐carbonitrile, an unsymmetrical fleximer. One aromatic ring and a heterocyclic ring (pyridone) are linked through trimethylene linker in this compound. The non‐covalent interactions observed in the solid state are studied using Hirshfeld surface and fingerprint analyses. The molecular solid is stabilized by C─H─O, C─H…N, C─H─л, and л─л interactions. Interaction energies for the most significant nonbonded contacts were calculated using CrystalExplorer17.
Investigation of lightning ignition characteristics based on an impulse current generator
Authors: Feng Junwei , Shen Hao , Liang Dong 
Published: December 2019

AbstractLightning strike is an important ignition source of forest fires. Artificial lightning discharge is a method for studying lightning fires. However, there is not enough data on the ignition of combustible materials caused by artificial lightning discharge. Previous studies on lightning ignition have focused on the heating and ignition effects of long continuing current (LCC), but the function of the impulse current that occurs before the LCC has not been taken into account. In this paper, an impulse current generator of 8/20 μs was used to simulate the ignition effect of impulse current on conifer needle beds. Different current waveforms have different ignition characteristics. We compared five kinds of conifer needle beds. The average of the current needed to ignite the needle bed of Larix gmelinii (Ruprecht) Kuzeneva was the smallest, and the average of the breakdown voltage was the smallest for the needle bed of Pinus massoniana Lamb. The total energy input to the conifer needle beds was fitted as a multiple log‐linear regression model. The heating energy proportion value varies with different bulk densities, current amplitudes, and moisture contents. Based on this data, the heating energy of the impulse current transferred to the needles can be predicted. This information in conjunction with previous research on LCC was used to derive a lightning ignition prediction model of the full waveform for conifer needle beds.
VARIATION OF POLYCYCLIC AROMATIC HYDROCARBON (PAH) CONTENTS IN THE VADOSE ZONE AND GROUNDWATER UNDER LONG‐TERM IRRIGATION USING RECLAIMED WATER
Authors: Hu Yaqi , Wu Wenyong , Xu Di , Liu Honglu 
Published: December 2019

AbstractUsing reclaimed water for agricultural irrigation is one of the most important measures for alleviating the global water crisis. The polycyclic aromatic hydrocarbon (PAH) vertical distribution characteristics in the vadose zone under long‐term reclaimed water irrigation and the corresponding impact on groundwater were studied by conducting a simulation experiment in the south‐east suburb of Beijing. The simulation experiment designed two different long‐term reclaimed water irrigation years, which were 98 and 236 years, respectively. The results showed that both treatments had a total PAH contents close to the background values (245–253 μg kg‾¹) and the long‐term reclaimed water irrigation did not result in a considerable PAH accumulation in soil profiles, which was supposed to be largely associated with the low PAH content of reclaimed water. The sources of PAH contamination in the vadose zone were mainly the combustion of fossil fuels and biomass by analysis of PAH isomer ratios. The total PAH contents in groundwater after percolation through the reclaimed water irrigation area was no more than 0.16 μg l‾¹ and the PAH removal rate of the vadose zone reached 97.7%. We stated that the vadose zone in the study area has excellent pollution prevention properties for PAHs under long‐term high‐quality reclaimed water irrigation. © 2019 John Wiley & Sons, Ltd.
Monitoring the phase evolution in LiCoO2 electrodes during battery cycles using in‐situ neutron diffraction technique
Authors: Jena Anirudha , Lee Po‐Han , Pang Wei Kong , Hsiao Kuang‐Che , Peterson Vanessa K. , Darwish Tamim , Yepuri Nageshwar , Wu She‐Huang , Chang Ho , Liu Ru‐Shi 
Published: December 2019

AbstractLiCoO2 (LCO) with average particle distribution of 8 μm (LCO‐A) and 11 μm (LCO‐B) exhibit substantial differences in cycle performance. The half‐cells have similar first‐cycle discharge capacities of 173 and 175 mAh/g at 0.25 C, but after 100 cycles, the discharge capacities are substantially different, that is, 114 and 141 mAh/g for LCO‐A and LCO‐B, respectively. Operando neutron powder diffraction of full LCO||Li4Ti5O12 batteries show differences in the LCO reaction mechanism underpinning the electrochemical behavior. LCO‐A follows a purely solid solution reaction during cycling compared to the solid solution and two‐phase reaction mechanism in LCO‐B. The absence of the two‐phase reaction in LCO‐A is consistent with a homogeneous distribution of Li throughout the particle. The two‐phase reaction in LCO‐B reflects two distinguishable distributions of Li within the particles. The faster capacity decay in LCO‐A is correlated to an increase in electrode cracking during battery cycles.
The role of temperature, pH and nutrition in process development of the unique oleaginous yeast Metschnikowia pulcherrima
Authors: Abeln Felix , Chuck Christopher J 
Published: December 2019

AbstractBACKGROUNDLipids produced from oleaginous yeasts are a promising alternative to terrestrial oils. Despite promising cellular yields of lipid however, an industrial process remains elusive. One key processing bottleneck is the need to provide nutrient‐rich conditions for cellular growth and then extended nutrient‐depleted conditions for lipid accumulation. Surprisingly, investigations detailing process development, particularly with a focus on kinetics, are rare in this field.RESULTSIn this investigation we report on the unique oleaginous yeast Metschnikowia pulcherrima, where lipid accumulation ≥ 29.8% (w/w) was achieved without apparent nutrient limitation. The process was developed in stirred tank reactors through determining the influence of temperature, pH and nutrition on lipid production. A temperature of up to 25 °C and initial pH 5 could be applied to enhance initial reaction kinetics. Through the increased supply of yeast extract of up to 5% (w/w) of glucose, a maximum lipid production rate of 0.60 g L−1 h−1 (4 h‐average), productivity of 0.29 g L−1 h−1, and yield of 0.17 g g−1 glucose were achieved – the highest yet recorded with this yeast. Suitable to combat the excessive secretion of polyols of up to 0.11 g g−1 glucose was an excess nutrient supply as well as a low cultivation temperature of 15 °C and moderate pH 5.CONCLUSIONSThis study demonstrates that the lack of a starvation stage, coupled with effective process development is required for oleaginous yeasts to achieve the yields and productivities required for commercial lipid production. © 2019 Society of Chemical Industry
Design thinking among first‐year and senior engineering students: A cross‐sectional, national study measuring perceived ability
Authors: Coleman Emma , Shealy Tripp , Grohs Jacob , Godwin Allison 
Published: December 2019

AbstractBackgroundPrior researchers developed an instrument to measure perceived design thinking ability of first‐year students interested in engineering, and they validated the instrument through exploratory factor analysis.Purpose/HypothesisOur study uses the previously developed instrument to evaluate perceived design thinking ability of senior engineering students. We make a cross‐sectional comparison of this measure on a national scale.Design/MethodWe surveyed a national sample of senior engineering students in 2018 and conducted a cross‐sectional comparison with results from a 2012 national sample of first‐year students who were interested in declaring an engineering major. Two‐way analysis of variance tests compared average design thinking scores across sample groups. Confirmatory factor analysis was conducted to improve the design thinking instrument.ResultsFirst‐year students who intended to declare an engineering major score significantly higher (2.80) on the design thinking scale than senior engineering students (2.59) with a medium effect size of 0.4. The senior engineering sample performs significantly worse on the feedback seeking and experimentalism instrument items, but significantly better on the integrative thinking and collaboration items. We found no significant differences in perceived design thinking ability among engineering disciplines among senior students.ConclusionsFeedback seeking and experimentalism are traits that engineering educators should develop in their students to improve perceived design thinking ability. Incorporation of user‐centered design and divergent thinking in the engineering classroom are recommended as avenues to foster feedback seeking and experimentalism. We also offer recommendations to improve the design thinking instrument for future research.