bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Optimally Performing Fischer–Tropsch Catalyst
Authors: Filot Ivo A. W. , van Santen Rutger A. , Hensen Emiel J. M. 
Published: August 2014

AbstractMicrokinetics simulations are presented based on DFT‐determined elementary reaction steps of the Fischer–Tropsch (FT) reaction. The formation of long‐chain hydrocarbons occurs on stepped Ru surfaces with CH as the inserting monomer, whereas planar Ru only produces methane because of slow CO activation. By varying the metal–carbon and metal–oxygen interaction energy, three reactivity regimes are identified with rates being controlled by CO dissociation, chain‐growth termination, or water removal. Predicted surface coverages are dominated by CO, C, or O, respectively. Optimum FT performance occurs at the interphase of the regimes of limited CO dissociation and chain‐growth termination. Current FT catalysts are suboptimal, as they are limited by CO activation and/or O removal.
Modulatory Effects of CD14+CD16++ Monocytes on CD14++CD16− Monocytes: A Possible Explanation of Monocyte Alterations in Systemic Lupus Erythematosus
Authors: Burbano C. , Vasquez G. , Rojas M. 
Published: August 2014

ObjectiveIn various chronic inflammatory processes, both the proportion and numbers of monocyte subsets are altered. In systemic lupus erythematosus (SLE), this has not been clearly determined. The monocyte subpopulations in patients with SLE, patients with other autoimmune diseases, and healthy controls were evaluated. The effects of nonclassic monocytes and apoptotic cells (ACs) on the differentiation and function of CD14++CD16− monocytes were also studied.MethodsMonocyte subpopulations derived from the blood samples of SLE patients (n = 88), patients with other autoimmune diseases (n = 37), and healthy control subjects (n = 61) were separated by fluorescence‐activated cell sorting. To evaluate the effect of CD14+CD16++ monocytes and ACs on the differentiation of CD14++CD16− monocytes, we developed a coculture model of highly purified sorted monocyte subpopulations, which were reconstituted with defined proportions of CD14++CD16− and CD14+CD16++ monocytes in the presence or absence of ACs. After differentiation into macrophages, CD3+ lymphocytes were added, and the proliferating cells and CD3+IFNγ+ cells were evaluated. A cytokine bead array panel was used to test the coculture supernatants.ResultsThere was a reduction in CD14+CD16++ monocytes in patients with active SLE. Monocytes from SLE patients had decreased expression of HLA–DR and decreased ability to bind and phagocytize ACs. In healthy controls, but not SLE patients, treatment with macrophages derived from CD14+CD16++ monocytes reduced T cell proliferation and proliferating CD3+IFNγ+ cells and increased the accumulation of tumor necrosis factor α, interleukin‐10 (IL‐10), and IL‐1β.ConclusionOur findings show that CD14+CD16++ monocytes, a population that is reduced and nonfunctional in SLE patients, have modulatory effects on CD14++CD16− monocytes and T cells.
Efficient hydroxyproline production from glucose in minimal media by Corynebacterium glutamicum
Authors: Falcioni Francesco , Bühler Bruno , Schmid Andreas 
Published: August 2014

ABSTRACTThe efficient coupling of biotransformation steps to an existing fermentation pathway is an interesting strategy to expand the product portfolio of Corynebacterium glutamicum as whole‐cell biocatalyst. This is especially challenging if the biotransformation step comprises a direct link to central metabolism, as in the case of α‐ketoglutarate‐dependent oxygenase catalysis. Aiming at trans‐4‐hydroxy‐L‐proline (Hyp) production from glucose in a minimal medium, the proline‐4‐hydroxylase gene from Dactylosporangium sp. strain RH1 was introduced into a proline‐producing, isoleucine‐bradytroph C. glutamicum strain. The production of proline was found to be induced by isoleucine limitation. Proline and Hyp production were found to depend differently on isoleucine limitation. Severe isoleucine limitation was shown to result in proline accumulation and low hydroxylation rates both in batch and continuous cultivation set‐ups. The investigation of different steady states with various glucose/isoleucine molar ratios revealed that optimal conditions for Hyp production are met around a molar ratio of 46:1, where isoleucine limitation is sufficient to trigger proline production but the hydroxylation rate is high enough to convert the majority of formed proline to Hyp. A high cell‐density fed‐batch set‐up was designed, capable of producing 7.1 g L−1 of Hyp from glucose in 23 h with 98.5% conversion of proline to Hyp. Reaction engineering, specifically the fine‐tuning of the glucose/isoleucine concentration ratio, enabled control of the fermentation profile and thus the accumulation of the desired product Hyp from glucose in minimal and defined media. Biotechnol. Bioeng. 2015;112: 322–330. © 2014 Wiley Periodicals, Inc.
Simultaneous determination of caffeic acid and its major pharmacologically active metabolites in rat plasma by LC‐MS/MS and its application in pharmacokinetic study
Authors: Wang Xiangyang , Li Wei , Ma Xiaohui , Chu Yang , Li Shuming , Guo Jiahua , Jia Yumeng , Zhou Shuiping , Zhu Yonghong , Liu Changxiao 
Published: August 2014

AbstractA simple, sensitive and selective high‐performance liquid chromatography electrospray ionization tandem mass spectrometry (LC‐MS/MS) method was developed for simultaneous determination and pharmacokinetic study of caffeic acid (CA) and its active metabolites. The separation with isocratic elution used a mobile phase composed of methanol and water (containing 0.1% formic acid) at a flow rate of 0.2 mL/min. The detection of target compounds was done in selected reaction monitoring (SRM) mode. The SRM detection was operated in the negative electrospray ionization mode using the transitions m/z 179 ([M − H]−) → 135 for CA, m/z 193 ([M − H]−) → 134.8 for ferulic acid and isoferulic acid and m/z 153 ([M − H]−) → 108 for protocatechuic acid. The method was linear for all analytes over the investigated range with all correlation coefficients 0.9931. The lower limits of quantification were 5.0 ng/mL for analytes. The intra‐ and inter‐day precisions (relative standard deviation) were <5.86 and <6.52%, and accuracy (relative error) was between −5.95 and 0.35% (n = 6). The developed method was applied to study the pharmacokinetics of CA and its major active metabolites in rat plasma after oral and intravenous administration of CA. Copyright © 2014 John Wiley & Sons, Ltd.
Eltrombopag with gemcitabine‐based chemotherapy in patients with advanced solid tumors: a randomized phase I study
Authors: Winer Eric S. , Safran Howard , Karaszewska Boguslawa , Richards Donald A. , Hartner Lee , Forget Frederic , Ramlau Rodryg , Kumar Kirushna , Mayer Bhabita , Johnson Brendan M. , Messam Conrad A. , Mostafa Kamel Yasser 
Published: August 2014

AbstractPreventing chemotherapy‐induced thrombocytopenia could avoid chemotherapy dose reductions and delays. The safety and maximum tolerated dose of eltrombopag, an oral thrombopoietin receptor agonist, with gemcitabine‐based therapy was evaluated. Patients with advanced solid tumors and platelets ≤300 × 109/L receiving gemcitabine plus cisplatin or carboplatin (Group A) or gemcitabine monotherapy (Group B) were randomized 3:1 to receive eltrombopag or placebo at a starting dose of 100 mg daily administered on days −5 to −1 and days 2–6 starting from cycle 2 of treatment. Nineteen patients (Group A, n = 9; Group B, n = 10) received eltrombopag 100 mg and seven (Group A, n = 3; Group B, n = 4) received matching placebo. Nine eltrombopag patients in Group A and eight in Group B had 38 and 54 occurrences of platelet counts ≥400 × 109/L, respectively. Mean platelet nadirs across cycles 2–6 were 115 × 109/L and 143 × 109/L for eltrombopag‐treated patients versus 53 × 109/L and 103 × 109/L for placebo‐treated patients in Groups A and B, respectively. No dose‐limiting toxicities were reported for eltrombopag; however, due to several occurrences of thrombocytosis, a decision was made not to dose‐escalate eltrombopag to >100 mg daily. In Groups A and B, 14% of eltrombopag versus 50% of placebo patients required chemotherapy dose reductions and/or delays for any reason across cycles 3–6. Eltrombopag 100 mg once daily administered 5 days before and after day 1 of chemotherapy was well tolerated with an acceptable safety profile, and will be further tested in a phase II trial. Fewer patients receiving eltrombopag required chemotherapy dose delays and/or reductions compared with those receiving placebo.
Chemistry of Guanidinate‐Stabilised Diboranes: Transition‐Metal‐Catalysed Dehydrocoupling and Hydride Abstraction
Authors: Wagner Arne , Litters Sebastian , Elias Jana , Kaifer Elisabeth , Himmel Hans‐Jörg 
Published: August 2014

AbstractHerein, we analyse the catalytic boron–boron dehydrocoupling reaction that leads from the base‐stabilised diborane(6) [H2B(hpp)]2 (hpp=1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐a]pyrimidinate) to the base‐stabilised diborane(4) [H2B(hpp)]2. A number of potential transition‐metal precatalysts was studied, including transition‐metal complexes of the product diborane(4). The synthesis and structural characterisation of two further examples of such complexes is presented. The best results for the dehydrocoupling reactions were obtained with precatalysts of Group 9 metals in the oxidation state of +I. The active catalyst is formed in situ through a multistep process that involves reduction of the precatalyst by the substrate [H2B(hpp)]2, and mechanistic investigations indicate that both heterogeneous and (slower) homogeneous reaction pathways play a role in the dehydrocoupling reaction. In addition, hydride abstraction from [H2B(hpp)]2 and related diboranes is analysed and the possibility for subsequent deprotonation is discussed by probing the protic character of the cationic boron–hydrogen compounds with NMR spectroscopic analysis.
Electrofluorochromic Detection of Cyanide Anions Using a Nanoporous Polymer Electrode and the Detection Mechanism
Authors: Ding Guoqiang , Lin TingTing , Zhou Rui , Dong Yuliang , Xu Jianwei , Lu Xuehong 
Published: August 2014

AbstractAn electrofluorochromic (EFC) conjugated copolymer (PEFC) containing carbazole and benzothiadiazole (BTD) moieties is synthesized through Suzuki coupling followed by electrochemical polymerization, resulting in a nanoporous EFC polymer electrode. The electrode exhibits high sensitivity and selectivity in the EFC detection of cyanide anions (CN−) in largely aqueous electrolyte (67 vol % water) because electrochemical oxidation of PEFC leads to significant fluorescence quenching, and the presence of different concentrations (1 to 100 μM) of CN− in the electrolyte can weaken the oxidative quenching to substantially different extents. Although PEFC is hydrophobic in the neutral state, it is converted to radical cation/dication states upon oxidation, rendering the PEFC some hydrophilicity. Moreover, its nanoporous morphology provides a large surface area and short diffusion distance, facilitating the movement of CN− in the electrolyte into the PEFC film to interact with receptors. Density functional theory calculations show that the noncovalent interaction between electron‐deficient BTD and nucleophilic CN− is energy favorable in the oxidized states in both aqueous and organic media, suggesting that the specific π−–π+ interaction plays the main role in the CN− detection.
Efficient Pd‐Catalyzed Allene Synthesis from Alkynes and Aryl Bromides through an Intramolecular Base‐Assisted Deprotonation (iBAD) Mechanism
Authors: Nella Natalie , Parker Evelyne , Hitce Julien , Larini Paolo , Jazzar Rodolphe , Baudoin Olivier 
Published: August 2014

AbstractAn optimized ligand‐controlled palladium‐catalyzed allene synthesis starting from alkynes and aryl bromides giving rise to allene products in a simple and direct manner is described. The methodology is performed in an inter‐ and intramolecular fashion with unprecedented scope and excellent yields. Based on mechanistic investigations and on DFT calculations, the role played by the carboxylic additive (i.e., PivOH) in controlling the selectivity of the reaction is discussed, allowing us to propose an intramolecular base‐assisted deprotonation (iBAD) mechanism for this process.
Highly Enantioselective Cross‐Aldol Reactions of Acetaldehyde Mediated by a Dual Catalytic System Operating under Site Isolation
Authors: Fan Xinyuan , Rodríguez‐Escrich Carles , Wang Shoulei , Sayalero Sonia , Pericàs Miquel A. 
Published: August 2014

AbstractPolystyrene‐supported (PS) diarylprolinol catalysts 1 a (Ar=phenyl) and 1 b (Ar=3,5‐bis(trifluoromethyl)phenyl) have been developed. Operating under site‐isolation conditions, PS‐1 a/1 b worked compatibly with PS‐bound sulfonic acid catalyst 2 to promote deoligomerization of paraldehyde and subsequent cross‐aldol reactions of the resulting acetaldehyde in one pot, affording aldol products in high yields with excellent enantioselectivities. The effect of water on the performance of the catalytic system has been studied and its optimal amount (0.5 equiv) has been determined. The dual catalytic system (1/2) allows repeated recycling and reuse (10 cycles). The potential of this methodology is demonstrated by a two‐step synthesis of a phenoperidine analogue (68 % overall yield; 98 % ee) and by the preparation of highly enantioenriched 1,3‐diols 4 and 3‐methylamino‐1‐arylpropanols 5, key intermediates in the synthesis of a variety of druglike structures.
Organometallic B12–DNA Conjugate: Synthesis, Structure Analysis, and Studies of Binding to Human B12‐Transporter Proteins
Authors: Hunger Miriam , Mutti Elena , Rieder Alexander , Enders Barbara , Nexo Ebba , Kräutler Bernhard 
Published: August 2014

AbstractDesign, synthesis, and structural characterization of a B12‐octadecanucleotide are presented herein, a new organometallic B12–DNA conjugate. In such covalent conjugates, the natural B12 moiety may be a versatile vector for controlled in vivo delivery of oligonucleotides to cellular targets in humans and animals, through the endogenous B12 transport systems. Binding of the organometallic B12 octadecanucleotide to the three important human proteins of B12 transport was studied, to examine its structural suitability for the task of eventual in vivo oligonucleotide delivery. Binding was efficient with transcobalamin (TC), but not so efficient with the homologous glycoproteins intrinsic factor and haptocorrin. Binding of the B12 octadecanucleotide to TC suggests the capacity of the B12 moiety to serve as a natural vector for specific transport of single stranded, organometallic oligonucleotide loads from the blood stream into cells.
Late‐Stage Diversification of Peptides by Metal‐Free CH Arylation
Authors: Zhu Yingjun , Bauer Michaela , Ploog Jasper , Ackermann Lutz 
Published: August 2014

AbstractThe bioorthogonal late‐stage diversification of functionalized oligopeptides was accomplished through a metal‐free, site‐selective CH arylation of engineered indole derivatives under mild reaction conditions.
[Au]/[Pd] Multicatalytic Processes: Direct One‐Pot Access to Benzo[c]chromenes and Benzo[b]furans
Authors: Oonishi Yoshihiro , Gómez‐Suárez Adrián , Martin Anthony R. , Makida Yusuke , Slawin Alexandra M. Z. , Nolan Steven P. 
Published: August 2014

AbstractA new synthetic protocol that combines the advantages offered by eco‐friendly solvent‐free reactions and sequential transformations is reported. This strategy offers straightforward access to benzo[c]chromenes and benzo[b]furans from commercially available starting materials. This two‐step, one‐pot strategy consists of an Au‐catalyzed hydrophenoxylation process followed by Pd‐catalyzed CH activation or Mizoroki–Heck reactions. The selectivity of the process towards CH activation or Mizoroki–Heck reaction can be easily tuned.
Obtaining Spruce Hemicelluloses of Desired Molar Mass by using Pressurized Hot Water Extraction
Authors: Rissanen Jussi V. , Grénman Henrik , Xu Chunlin , Willför Stefan , Murzin Dmitry Yu , Salmi Tapio 
Published: August 2014

AbstractThere is growing interest in utilizing galactoglucomannan, the main hemicellulose in softwoods, for various applications such as cosmetics, pharmaceuticals, textiles, alimentary, and health products, as well as for the production of fuels. For fuel production and for using the rare sugars as platform chemicals, the hemicelluloses need to be hydrolyzed to sugar monomers, and for this purpose, low‐molecular‐mass extracts are favorable. However, for the other applications high molecular masses are required, which presents an even greater challenge for extraction. The ability to optimize the extraction process according to the needs of further processing, by using solely water as the solvent, is a key issue in the environmentally friendly utilization of this versatile raw material. The goal of this work is to study how the average molar mass of hemicelluloses extracted from spruce sapwood can be influenced by altering the experimental conditions. The main parameters influencing the extraction and hydrolysis of the hemicelluloses, namely, extraction time, temperature, pH, and chip size, were studied. The results show that it is feasible to develop an extraction process for harvesting spruce hemicelluloses, also of large molar masses, for industrial applications by using pressurized hot water extraction.
A Custom Correlation Coefficient (CCC) Approach for Fast Identification of Multi‐SNP Association Patterns in Genome‐Wide SNPs Data
Authors: Climer Sharlee , Yang Wei , de las Fuentes Lisa , Dávila‐Román Victor G. , Gu C. Charles 
Published: August 2014

ABSTRACTComplex diseases are often associated with sets of multiple interacting genetic factors and possibly with unique sets of the genetic factors in different groups of individuals (genetic heterogeneity). We introduce a novel concept of custom correlation coefficient (CCC) between single nucleotide polymorphisms (SNPs) that address genetic heterogeneity by measuring subset correlations autonomously. It is used to develop a 3‐step process to identify candidate multi‐SNP patterns: (1) pairwise (SNP–SNP) correlations are computed using CCC; (2) clusters of so‐correlated SNPs identified; and (3) frequencies of these clusters in disease cases and controls compared to identify disease‐associated multi‐SNP patterns. This method identified 42 candidate multi‐SNP associations with hypertensive heart disease (HHD), among which one cluster of 22 SNPs (six genes) included 13 inSLC8A1(akaNCX1, an essential component of cardiac excitation‐contraction coupling) and another of 32 SNPs had 29 from a different segment ofSLC8A1. While allele frequencies show little difference between cases and controls, the cluster of 22 associated alleles were found in 20% of controls but no cases and the other in 3% of controls but 20% of cases. These suggest that both protective and risk effects on HHD could be exerted by combinations of variants in different regions ofSLC8A1, modified by variants from other genes. The results demonstrate that this new correlation metric identifies disease‐associated multi‐SNP patterns overlooked by commonly used correlation measures. Furthermore, computation time using CCC is a small fraction of that required by other methods, thereby enabling the analyses of large GWAS datasets.
Quantifying synoptic eddy feedback onto the low‐frequency flow associated with anomalous temperature events in January over China
Authors: Tan Gui‐Rong , Ren Hong‐Li , Chen Haishan 
Published: August 2014

ABSTRACTUsing a linear dynamic operator and the daily National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis data, the linearized part of the synoptic eddy feedback onto the low‐frequency flow (SELF) associated with cold/warm events in January over China is investigated. Composite stream function differences between the cold and warming events show that the anomalous temperature events are linked closely to the teleconnection pattern which is related to North Atlantic Oscillation (NAO) and accompanied with remarkable anomalies over Ural Mountain and the areas south to Lake Baikal. The significant eddy feedback exists as the episodes occur, which tends to induce a similar circulation pattern to the anomalous low‐frequency flow associated with the temperature episodes. Further, a linear SELF operator is used to estimate quantitatively the linearized part of the eddy feedback on the low‐frequency flow for the temperature events. Results show that the magnitude of the stream function anomalies (SFAs) induced by eddy forcing is bigger at higher latitudes than lower latitudes. The positive (negative) SFA can be induced where eddy‐vorticity fluxes converge (diverge) into the anomalous cyclonic (anticyclonic) circulation. Further analysis of differences in eddy feedback strength suggests that synoptic eddy feedback is more effective for the cold events than that for the warm events over North Atlantic, Ural Mountain, and the areas south to Lake Baikal. The SFA anomaly pattern over Ural Mountain and Lake Baikal associated with the anomalous temperature events in China will disappear without considering the eddy feedback. It suggests that the eddy feedback plays a very important role in maintaining the low‐frequency flow during the January anomalous temperature events.
Viewing‐angle‐enhanced integral imaging system using high‐refractive‐index medium and curved micro‐lens array
Authors: Liu Yao , Wang Qiong‐Hua , Ji Chao‐Chao , Luo Cheng‐Gao 
Published: August 2014

AbstractIn the integral imaging (II) system using a curved micro‐lens array (MLA), the viewing angle is limited by the gap mismatch. Here, we propose a system to decrease the gap mismatch for enhancing the viewing angle. In the proposed system, a layer of high‐refractive‐index medium is assembled between the display panel and the curved MLA. The principle of the proposed II system is studied in detail. Simulations based on ray tracing are performed, and the results show that the proposed II system can effectively enhance the viewing angle.
The effect of different utility measures on the cost‐effectiveness of bilateral cochlear implantation
Authors: Kuthubutheen Jafri , Mittmann Nicole , Amoodi Hosam , Qian Wei , Chen Joseph M. 
Published: August 2014

Objectives/HypothesisTo determine if the choice of health utility measure affects the incremental cost‐utility ratio (ICUR) when assessing the cost‐effectiveness of bilateral cochlear implantation (CI).Study DesignA scenario‐based estimate with three scenarios: 1) a patient with severe to profound sensorineural hearing loss with no intervention, 2) the same patient with a unilateral CI with average or better performance, and 3) the same patient with bilateral CIs with average or better performance.MethodsOne hundred and forty‐two subjects comprising preimplantees (n = 30), unilateral cochlear implantees (n = 30), bilateral implantees (n = 30), and healthcare professionals (n = 52). The four health utility instruments applied were the Health Utility Index Mark 3 (HUI3), European Quality of Life Questionnaire in 5 Domains (EQ5D), visual analog scale (VAS), and time trade‐off (TTO). Cost for each implant was based on a 25‐year time horizon, 50% discount for the second implant, and a 15% failure rate.ResultsUsing the HUI3, the utility gain from unilateral to bilateral implantation was 0.035 or 11.5% of the total utility gain. This ratio was higher using the other instruments: EQ5D (22.2%), VAS (35.0%), and TTO (41.4%). For the scenario of bilateral CI compared to no intervention, HUI3 ICUR estimates were the lowest, and for bilateral CI compared to unilateral CI, HUI3 ICUR estimates were the highest.ConclusionsThe choice of utility instrument in cost‐utility analysis of bilateral CI heavily influences whether the second implant is deemed cost‐effective. The HUI3 is the utility of choice in CI studies and is the most conservative.Level of Evidence4.Laryngoscope, 125:442–447, 2015