bluuebunny/crossref_metadata_2025_split huggingface dataset:
Miller–Urey Spark‐Discharge Experiments in the Deuterium World
Authors: Cooper Geoffrey J. T. , Surman Andrew J. , McIver Jim , Colón‐Santos Stephanie M. , Gromski Piotr S. , Buchwald Saskia , Suárez Marina Irene , Cronin Leroy 
Published: May 2017

AbstractWe designed and conducted a series of primordial‐soup Miller‐Urey style experiments with deuterated gases and reagents to compare the spark‐discharge products of a “deuterated world” with the standard reaction in the “hydrogenated world”. While the deuteration of the system has little effect on the distribution of amino acid products, significant differences are seen in other regions of the product‐space. Not only do we observe about 120 new species, we also see significant differences in their distribution if the two hydrogen isotope worlds are compared. Several isotopologue matches can be identified in both, but a large proportion of products have no equivalent in the corresponding isotope world with ca. 43 new species in the D world and ca. 39 new species in the H world. This shows that isotopic exchange (the addition of only one neutron) may lead to significant additional complexity in chemical space under otherwise identical reaction conditions.
Air‐Stable Manganese(I)‐Catalyzed C−H Activation for Decarboxylative C−H/C−O Cleavages in Water
Authors: Wang Hui , Lorion Mélanie M. , Ackermann Lutz 
Published: May 2017

AbstractThe decarboxylative C−H/C−O functionalization was accomplished by air‐ and water‐tolerant manganese(I) catalysis. The versatile C−H allylation occurred by facile organometallic C−H metalation on indoles, arenes, amino acids and synthetically meaningful aryl ketimines with ample substrate scope and high levels of chemo‐, site‐ and regio‐selectivity.
Oxidative Neutralization of Mustard‐Gas Simulants in an On‐Board Flow Device with In‐Line NMR Monitoring
Authors: Picard Baptiste , Gouilleux Boris , Lebleu Thomas , Maddaluno Jacques , Chataigner Isabelle , Penhoat Maël , Felpin François‐Xavier , Giraudeau Patrick , Legros Julien 
Published: May 2017

AbstractThe fast and effective neutralization of the mustard‐gas simulant 2‐chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea–H2O2 adduct/MeSO3H freshly prepared). The reaction progress can be monitored with an in‐line benchtop NMR spectrometer, allowing a real‐time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (tR=3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.
Zinc(II) complexes of Triaza and Amidinate ligands: Efficient initiators for the ring‐opening polymerization of ε‐Caprolactone and rac‐Lactide
Authors: Kirubakaran Bakthavachalam , Beesam Raghavendra , Nareddula Dastagiri Reddy 
Published: May 2017

Zinc complexes supported by tertiary 1,3,5‐triazapenta‐1,3‐dienate ligand (L1) and N‐benzoyl‐N′‐arylbenzamidinate [aryl =2,6‐diisopropylphenyl (L2), phenyl (L3)] ligands have been synthesized and characterized. The reaction of L1H with ZnEt2 affords a mononuclear zinc complex [L1ZnEt] (1) in good yield. Tetra nuclear zinc complex [(L1)2Zn4O(OAc)4] (2) is prepared by treating L1H with one equivalent of Zn(OAc)2 in toluene. Further, dinuclear zinc complexes [L2ZnEt]2 (3) and [L3ZnEt]2 (4) are obtained in good yields from L2H and L3H with ZnEt2 in toluene respectively. The complexes 1–4 have been characterized by 1H/13C NMR spectroscopy and single crystal X‐ray diffraction studies. All of the complexes have been explored for their catalytic activity toward the ring‐opening polymerization (ROP) of ε‐caprolactone. It has been found that complex 1 is an active catalyst for the polymerization of ε‐caprolactone in presence of a cocatalyst benzyl alcohol (BnOH). While complex 2 is as active as 1 there is no need for a cocatalyst for the polymerization to proceed. Dinuclear zinc complexes 3 and 4 show very high activity for the ROP of ε‐caprolactone (CL) and rac‐lactide (LA) without requiring a cocatalyst. The resultant polymers are found to have very high molecular weight (Mn = 296 X 103 g mol−1) and relatively narrow polydispersity index compared to 1 and 2.
Application of physiologically based pharmacokinetic modeling to predict drug disposition in pregnant populations
Authors: Jogiraju Vamshi Krishna , Avvari Suvarchala , Gollen Rakesh , Taft David R. 
Published: May 2017

AbstractPregnancy is associated with numerous physiological changes that influence absorption, distribution, metabolism and excretion. Moreover, the magnitude of these effects changes as pregnancy matures. For most medications, there is limited information available about changes in drug disposition that can occur in pregnant patients, yet most women are prescribed one or more medications during pregnancy. In this investigation, PBPK modeling was used to assess the impact of pregnancy on the pharmacokinetic profiles of three medications (metformin, tacrolimus, oseltamivir) using the Simcyp® simulator. The Simcyp pregnancy‐PBPK model accounts for the known physiological changes that occur during pregnancy. For each medication, plasma concentration–time profiles were simulated using Simcyp® virtual populations of healthy volunteers and pregnant patients. The predicted systemic exposure metrics (Cmax, AUC) were compared with published clinical data, and the fold error (FE, ratio of predicted and observed data) was calculated. The PBPK model was able to capture the observed changes in Cmax and AUC across each trimester of pregnancy compared with post‐partum for metformin (FE range 0.86–1.19), tacrolimus (FE range 1.03–1.64) and oseltamivir (FE range 0.54–1.02). Simcyp model outputs were used to correlate these findings with pregnancy‐induced alterations in renal blood flow (metformin, oseltamivir), hepatic CYP3A4 activity (tacrolimus) and reduced plasma protein levels and hemodilution (tacrolimus). The results illustrate how PBPK modeling can help to establish appropriate dosing guidelines for pregnant patients and to predict potential changes in systemic exposure during pregnancy for compounds undergoing clinical development.
Enhanced d‐lactic acid production by recombinant Saccharomyces cerevisiae following optimization of the global metabolic pathway
Authors: Yamada Ryosuke , Wakita Kazuki , Mitsui Ryosuke , Ogino Hiroyasu 
Published: May 2017

ABSTRACTUtilization of renewable feedstocks for the production of bio‐based chemicals such as d‐lactic acid by engineering metabolic pathways in the yeast Saccharomyces cerevisiae has recently become an attractive option. In this study, to realize efficient d‐lactic acid production by S. cerevisiae, the expression of 12 glycolysis‐related genes and the Leuconostoc mesenteroides d‐LDH gene was optimized using a previously developed global metabolic engineering strategy, and repeated batch fermentation was carried out using the resultant strain YPH499/dPdA3‐34/DLDH/1‐18. Stable d‐lactic acid production through 10 repeated batch fermentations was achieved using YPH499/dPdA3‐34/DLDH/1‐18. The average d‐lactic acid production, productivity, and yield with 10 repeated batch fermentations were 60.3 g/L, 2.80 g/L/h, and 0.646, respectively. The present study is the first report of the application of a global metabolic engineering strategy for bio‐based chemical production, and it shows the potential for efficient production of such chemicals by global metabolic engineering of the yeast S. cerevisiae. Biotechnol. Bioeng. 2017;114: 2075–2084. © 2017 Wiley Periodicals, Inc.
Quantitative proteome profiles help reveal efficient xylose utilization mechanisms in solventogenic Clostridium sp. strain BOH3
Authors: Basu Anindya , Xin Fengxue , Lim Teck Kwang , Lin Qingsong , Yang Kun‐Lin , He Jianzhong 
Published: May 2017

ABSTRACTDevelopment of sustainable biobutanol production platforms from lignocellulosic materials is impeded by inefficient five carbon sugar uptake by solventogenic bacteria. The recently isolated Clostridium sp. strain BOH3 is particularly advantaged in this regard as it serves as a model organism which can simultaneously utilize both glucose and xylose for high butanol (>15 g/L) production. Strain BOH3 was, therefore, investigated for its metabolic mechanisms for efficient five carbon sugar uptake using a quantitative proteomics based approach. The proteomics data show that proteins within the CAC1341‐1349 operon play a pivotal role for efficient xylose uptake within the cells to produce butanol. Furthermore, up‐regulation of key enzymes within the riboflavin synthesis pathway explained that xylose could induce higher riboflavin production capability of the bacteria (e.g., ∼80 mg/L from glucose vs. ∼120 mg/L from xylose). Overall results from the present experimental approach indicated that xylose‐fed BOH3 cultures are subjected to high levels of redox stress which coupled with the solvent stress—trigger a sporulation response within the cells earlier than the glucose‐fed cultures. The study lays the platform for metabolic engineering strategies in designing organisms for efficient butanol and other value‐added chemicals such as riboflavin production. Biotechnol. Bioeng. 2017;114: 1959–1969. © 2017 Wiley Periodicals, Inc.
A comparative pharmacokinetic study of three flavonoids and three anthraquinones in normal and gastrointestinal motility disorders rat plasma after the oral administration of Wei‐Chang‐Shu tablet using high‐performance liquid chromatography–tandem mass spectrometry
Authors: Ren Yan , Zhao Weiwei , Zhao Juanjuan , Chen Xiangming , Yu Chen , Liu Mengan 
Published: May 2017

AbstractA simple, fast and reliable high‐performance liquid chromatography–tandem mass spectrometry method was developed and validated for the simultaneous quantification and pharmacokinetic study of three flavonoids (liquiritigenin, isoliquiritigenin and formononetin) and three anthraquinones (emodin, rhein and aloe‐emodin), which are the bioactive ingredients of Wei‐Chang‐Shu tablet found in rat plasma. After extraction by liquid–liquid extraction with ethyl acetate, chromatographic separation was achieved on an Agilent Zorbax SB‐C18 column (4.6 × 150 mm, 5 μm) at a flow rate of 1 mL/min by gradient elution using 0.1% aqueous acetic acid and acetonitrile. The detection was performed using a triple quadrupole mass spectrometer equipped with electrospray ionization source in the negative ionization and selected reaction monitoring mode. Method validation was performed in terms of specificity, carryover, linearity (r > 0.99), intra−/inter‐day precision (1.0–10.1%), accuracy (relative error, <7.6%), stability (0.6–13.2%), extract recovery (74.9–91.9%) and matrix effect (89.1–109%). The lower limits of quantification of the six analytes varied from 0.92 to 10.4 ng/mL. The validated method was successfully applied to compare the pharmacokinetic properties of Wei‐Chang‐Shu tablet in normal rats and in rats with gastrointestinal motility disorders. The results indicated that there were obvious differences in the pharmacokinetic behavior between normal and model rats. This study will be helpful in the clinical application of Wei‐Chang‐Shu tablet.
Identification of differential metabolic characteristics between tumor and normal tissue from colorectal cancer patients by gas chromatography–mass spectrometry
Authors: Ning Wu , Li Haijing , Meng Fanqiang , Cheng Jianhua , Song Xin , Zhang Guochao , Wang Wenyue , Wu Shengming , Fang Junjian , Ma Kunpeng , Yang Jie , Pei Dongpo , Dong Fangting 
Published: May 2017

AbstractColorectal cancer (CRC) is one of the most common human malignancies and encompasses cancers of the colon and rectum. Although the gold‐standard colonoscopy screening method is effective in detecting CRC, this method is invasive and can result in severe complications for patients. The purpose of this study was to determine differences in metabolites between CRC and matched adjacent nontumor tissues from CRC patients, to identify potential biomarkers that may be informative and developed screening methods. Metabolomic analysis was performed on clinically localized CRC tissue and matched adjacent nontumor tissue from 20 CRC patients. Unsupervised analysis, supervised analysis, univariate analysis and pathway analysis were used to identify potential metabolic biomarkers of CRC. The levels of 25 metabolites in CRC tissues were significantly altered compared with the matched adjacent nontumor tissues. Four metabolites (lactic acid, alanine, phosphate and aspartic acid) demonstrated good area under the curve of receiver‐operator characteristic with acceptable sensitivities and specificities, indicating their potential as important biomarkers for CRC. Alterations of amino acid metabolism and enhanced glycolysis may be major factors in the development and progression of CRC. Lactic acid, alanine, phosphate, and aspartic acid could be effective diagnostic indicators for CRC.
Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton‐Transfer Dynamics of the Boroalkoxide Intermediate
Authors: Heshmat Mojgan , Privalov Timofei 
Published: May 2017

AbstractBy using transition‐state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C6F5)3B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4‐dioxane or THF). For the solvent‐assisted H2 splitting at the carbonyl carbon atom of (C6F5)3B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born–Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C6F5)3B–alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C6F5)3B, as a catalyst, namely, 1) the step of H2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C6F5)3B–ketone adducts in which (C6F5)3B is the “Lewis acid promoter”, 2) the transfer of the solvent‐bound proton to the oxygen atom of the (C6F5)3B–alkoxide intermediate giving the (C6F5)3B–alcohol adduct, and 3) the SN2‐style displacement of the alcohol by a ketone or a Lewis basic solvent molecule.
Facile Preparation of a Stable Fe3O4@LDH@NiB Magnetic Core‐Shell Nanocomposite for Hydrogenation
Authors: Gao Xuejia , Niu Libo , Qiao Xianliang , Feng Wenhui , Cao Yingying , Bai Guoyi 
Published: May 2017

AbstractA novel NiB deposited layered double hydroxide (LDH) coated ferroferric oxide (Fe3O4@LDH@NiB) magnetic core‐shell nanocomposite was successfully fabricated by the combination of coprecipitation and impregnation‐reduction. During the Fe3O4@LDH preparation, a facile template‐free approach was employed to introduce the LDH shell, which was more efficient than the conventional method for the preparation of mesoporous materials that always needs to introduce and remove templates. The resulted Fe3O4@LDH has a relatively high surface area and abundant surface hydroxyl group, which can adsorb metal ions, making it favorable to disperse and stabilize the active Ni species, as demonstraed by TEM, XPS, FT‐IR and BET characterizations. Therefore, it exhibited good activity in the selective hydrogenation of cinnamic acid to hydrocinnamic acid with the conversion and selectivity both approaching to 100%. Notably, the obtained Fe3O4@LDH@NiB can be easily separated by an external magnetic field and recycled eleven times without appreciable loss of its initial catalytic activity.
Semi‐asynchronous approximate parallel DEVS simulation of web search engines
Authors: Inostrosa‐Psijas Alonso , Gil‐Costa Veronica , Marin Mauricio ,  Wainer Gabriel 
Published: May 2017

SummaryDiscrete Event System Specification (DEVS) is a formalism for the modeling and analysis of discrete event systems. Parallel DEVS (PDEVS) is an extension of DEVS for supporting Parallel and Discrete Event Simulation, which is a powerful tool for evaluating the performance of large scale systems. In this work, we propose an optimistic approximate and semi‐asynchronous parallel strategy. The level of optimism is efficiently managed throughout the simulation execution, and it is automatically adjusted based on the simulation evolution. Load balance and model partitioning is automatically made by means of an algorithm that takes advantage of the communication pattern of the simulated model. Our proposal is designed for Web search engines, which are complex and highly optimized systems devised to operate on large clusters of processors and dealing with dynamic and unpredictable user query bursts. The results show that our proposal is able to reduce both execution times and memory usage of standard optimistic simulations of Web search engine models, at the expense of small errors.
Microwave‐absorbing properties of strontium ferrites prepared via sol‐gel method
Authors: Xing Liu , Shun‐kang Pan , Xing Zhong , Li‐chun Cheng 
Published: May 2017

Strontium ferrites were prepared by sol‐gel method, the phase structure, morphology, and microwave absorbing properties of the samples were studied by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and vector network analyzer (VNA). The results show that with increasing sintering temperature, the wave‐absorption peak frequency moves towards low‐frequency direction and the reflection loss value decreases first, and then increases. At the same sintering temperature (1200 °C) and different holding time (2h, 4h, 6h, 8h), the ferrites have the same Z‐type phase structure. With increasing holding time, the absorption peak frequency of the ferrites shift towards low‐frequency region, and the minimum reflectivity value decreases first and increases afterwards, and the ferrite holding at 1200 °C for 4 h has the best microwave‐absorbing property.
A QA Program for MRD Testing Demonstrates That Systematic Education Can Reduce Discordance Among Experienced Interpreters
Authors: Keeney Michael , Wood Brent L. , Hedley Benjamin D. , DiGiuseppe Joseph A. , Stetler‐Stevenson Maryalice , Paietta Elisabeth , Lozanski Gerard , Seegmiller Adam C. , Greig Bruce W. , Shaver Aaron C. , Mukundan Lata , Higley Howard R. , Sigman Caroline C. , Kelloff Gary , Jessup J. Milburn , Borowitz Michael J. 
Published: May 2017

BackgroundMinimal residual disease (MRD) in B lymphoblastic leukemia (B‐ALL) by flow cytometry is an established prognostic factor used to adjust treatment in most pediatric therapeutic protocols. MRD in B‐ALL has been standardized by the Children's Oncology Group (COG) in North America, but not routine clinical labs. The Foundation for National Institutes of Health sought to harmonize MRD measurement among COG, oncology groups, academic, community and government, laboratories.MethodsListmode data from post‐induction marrows were distributed from a reference lab to seven different clinical FCM labs with variable experience in B‐ALL MRD. Labs were provided with the COG protocol. Files from 15 cases were distributed to the seven labs. Educational sessions were implemented, and 10 more listmode file cases analyzed.ResultsAmong 105 initial challenges, the overall discordance rate was 26%. In the final round, performance improved considerably; out of 70 challenges, there were five false positives and one false negative (9% discordance), and no quantitative discordance. Four of six deviations occurred in a single lab. Three samples with hematogones were still misclassified as MRD.ConclusionsDespite the provision of the COG standardized analysis protocol, even experienced laboratories require an educational component for B‐ALL MRD analysis by FCM. Recognition of hematogones remains challenging for some labs when using the COG protocol. The results from this study suggest that dissemination of MRD testing to other North American laboratories as part of routine clinical management of B‐ALL is possible but requires additional educational components to complement standardized methodology. © 2017 International Clinical Cytometry Society
Sulfur Tolerant LSCM‐based Composite Cathode for High Temperature Electrolysis/Co‐electrolysis of H2O and CO2
Authors: Lim C. K. , Liu Q. , Zhou J. , Sun Q. , Chan S. H. 
Published: May 2017

AbstractThe cathode performance of various LSCM‐based composites for high temperature H2O electrolysis has been studied by examining their electrochemical behavior under current loading using three‐electrode electrolysis cells with Pt as counter and reference electrodes. Experimental results among pure LSCM, LSCM–GDC, LSCM–YSZ and LSCM–(GDC–YSZ) have shown that LSCM‐GDC exhibits the highest H2O electrolysis performance. The ratio between LSCM and GDC is further optimized and it is shown that the LSCM‐GDC with 50–50 wt.% for each component exhibits the highest performance. Benchmarking with a 60–40 wt.% Ni‐YSZ cathode have shown that the optimized LSCM–GDC cathode exhibits better performance for H2O electrolysis with a lower area specific resistance. Under a cathodic current of –0.1 A cm−2, the optimized LSCM–GDC cathode shows much slower degradation, about 10 times slower as compared to the Ni‐YSZ cathode when exposed to 10 ppm of SO2 for up to 72 h. All the above electrochemical tests have been conducted at 800 °C and 70/30 pH2O/pH2. Without the use of reducing agent, the optimized LSCM–GDC cathode also shows promising performance for co‐electrolysis of H2O and CO2 at high current densities and stable performance with 5 ppm of SO2 in the feedstock gas.
Incomplete cavernous sinus syndrome as the initial manifestation of a previously undetected metastatic prostate adenocarcinoma
Authors: Machío Castelló María , Escobar Montatixe Diego , Cenjor Español Carlos , Villacampa Aubá José Miguel , Montoya Bordón Julia , Carias Calix Rafael , Sáez Pinel Rafael 
Published: May 2017

AbstractBackgroundCavernous sinus syndrome presents as unilateral ophthalmoplegia associated with sympathetic denervation, pain, paresthesias, and V1 and V2 distribution numbness. The etiology may be vascular, inflammatory, infectious, and, less commonly, neoplastic (metastatic).MethodsWe report a patient with incomplete cavernous sinus syndrome as the initial manifestation of previously undetected metastatic prostate adenocarcinoma.ResultsA 59‐year‐old man presented with a 2‐month history of left hemicranial headaches with ptosis and binocular diplopia. Clinical evaluation found left third, fourth, and sixth cranial nerve palsy with mydriasis and ptosis. An MRI showed an enhancing lesion at the clivus with infiltration of left cavernous sinus. A trans‐sphenoidal biopsy was performed, leading to diagnosis of metastatic prostate adenocarcinoma. The patient underwent treatment and achieved clinical improvement.ConclusionsIn middle‐aged men, it is important to include metastatic prostate adenocarcinoma in the differential diagnosis of cavernous sinus syndrome, even in the absence of primary tumor diagnosis.