bluuebunny/crossref_metadata_2025_split huggingface dataset:
Biocatalytic Racemization Employing TeSADH: Substrate Scope and Organic Solvent Compatibility for Dynamic Kinetic Resolution
Authors: Popłoński Jarosław , Reiter Tamara , Kroutil Wolfgang 
Published: January 2018

AbstractRacemization in combination with a kinetic resolution is the base for a dynamic kinetic resolution (DKR). Biocatalytic racemization was successfully performed for a broad scope of sec‐alcohols by employing a single alcohol dehydrogenase (ADH) variant from Thermoanaerobacter pseudoethanolicus (formerly T. ethanolicus; TeSADH W110A I86A C295A). The catalyst employed as a lyophilized whole cell preparation or cell free extract, which tolerated various non‐water miscible organic solvents under micro‐aqueous or two‐phase conditions, whereby cyclohexane and n‐hexane suited best. Various concepts for combining the enzymatic racemization with an enzymatic kinetic resolution to achieve overall a bis‐enzymatic DKR were evaluated. A proof of concept showed a successful DKR with racemization in aqueous phase combined with acylation in the organic phase.
Copper–Cobalt–Cerium Ternary Oxide as an Additive to a Conventional Platinum‐Group‐Metal Catalyst for Automotive Exhaust Catalysis
Authors: Binder Andrew J. , Toops Todd J. , Parks James E. 
Published: January 2018

AbstractRecently, we reported on a ternary mixed‐oxide catalyst that showed low‐temperature CO oxidation activity under lean exhaust conditions without inhibition by hydrocarbons such as propene. However, the hydrocarbon oxidation activity of this Cu–Co–Ce (CCC) catalyst cannot be considered as a stand‐alone solution to low‐temperature automotive exhaust catalysis. To achieve both low‐temperature oxidation of pollutants and a reduction in the total platinum‐group‐metal (PGM) content, we examined a 50 % physical mixture of traditional Pt/Al2O3 and our CCC catalyst in two simulated exhaust protocols. Using this physical mixture, we were able to obtain equivalent or better hydrocarbon activity than the baseline Pt/Al2O3 catalyst with half the total PGM content as well as increased sulfur tolerance for the CCC component of the mixture. Diffuse reflectance infrared Fourier transform spectroscopy data confirmed that despite exposure of sulfur‐sensitive CCC to SO2, Cu+‐carbonyl binding sites could still be seen if the catalyst was mixed with Pt/Al2O3.
Ring‐Expanded N‐Heterocyclic Carbenes for Copper‐Mediated Azide–Alkyne Click Cycloaddition Reactions
Authors: Sebest Filip , Dunsford Jay J. , Adams Matthew , Pivot Jeremy , Newman Paul D. , Díez‐González Silvia 
Published: January 2018

AbstractA series of well‐defined copper(I) complexes bearing ring‐expanded N‐heterocyclic carbene (NHC) ligands has been applied to the azide–alkyne cycloaddition reaction. The obtained results notably showed that the six‐membered NHC ligands outperform well‐established five‐membered ones. [CuI(Mes‐6)] displayed a remarkable catalytic activity while respecting the strict criteria for click reactions.
Recent Membrane Developments for CO2 Separation and Capture
Authors: Norahim Nadia , Yaisanga Pacharaporn , Faungnawakij Kajornsak , Charinpanitkul Tawatchai , Klaysom Chalida 
Published: January 2018

AbstractIncreasing concerns on global warming and climate change have led to numerous attempts and advanced technology developments to tackle the problem of excessive greenhouse gases emitted to the atmosphere. One of the technical strategies receiving great attention is the application of membrane technology for greenhouse gas separation/capture. Such technology exhibits significant advantages over other conventional methods in terms of removal efficiency, compactness, and environmental friendliness. Many state‐of‐the‐art membrane developments as well as its applications to post‐combustion treatment, which could be a promising approach for reducing CO2 emission from point sources, are thoroughly reviewed. Furthermore, a comprehensive survey on the future perspective of membrane technologies as a potential solution for CO2 removal and utilization is provided.
Hierarchically Porous Multilayered Carbon Barriers for High‐Performance Li–S Batteries
Authors: Chang Zhi , Ding Bing , Dou Hui , Wang Jie , Xu Guiyin , Zhang Xiaogang 
Published: January 2018

AbstractAs one of the most promising energy storage devices, the practical application of lithium–sulfur batteries is limited by the low electrical conductivity of sulfur and the notable “shuttle effects” of sulfur‐based electrodes. In this work, we describe a hierarchically porous N‐doped zeolitic imidazolate framework‐8 (ZIF‐8)‐derived carbon nanosphere (N‐ZDC) with an outer shell and an inner honeycomb‐like interconnected nanosheet network as sulfur host material for high‐performance and long‐term lithium–sulfur batteries. The N‐ZDC serves as multilayered barrier against the dissolution of lithium polysulfides. The porously inner interconnected carbon network of the N‐ZDC facilitates the electron and ion transportation, ensures a high sulfur loading, and accommodates a volume expansion of the sulfur species. As a result, the optimized N‐ZDC4/S electrodes displayed high initial specific capacities of 1343, 1182, and 698 mAh g−1 at 0.5, 1, and 2 C, respectively, and an ultraslow capacity decay of only 0.048 % per cycle at 2 C over 800 cycles. Even with a high sulfur loading of 3.1 mg cm−2, N‐ZDC4/S still delivered a reversible capacity of 956 mAh g−1 and stabilizes at 544 mAh g−1 after 500 cycles at 0.5 C, revealing the great potential of the novel carbon nanospheres for energy storage application.
Spin Crossover in a Hexaamineiron(II) Complex: Experimental Confirmation of a Computational Prediction
Authors: Bernhardt Paul V. , Bilyj Jessica K. , Brosius Victor , Chernyshov Dmitry , Deeth Robert J. , Foscato Marco , Jensen Vidar R. , Mertes Nicole , Riley Mark J. , Törnroos Karl W. 
Published: January 2018

AbstractSingle crystal structural analysis of [FeII(tame)2]Cl2⋅MeOH (tame=1,1,1‐tris(aminomethyl)ethane) as a function of temperature reveals a smooth crossover between a high temperature high‐spin octahedral d6 state and a low temperature low‐spin ground state without change of the symmetry of the crystal structure. The temperature at which the high and low spin states are present in equal proportions is T1/2=140 K. Single crystal, variable‐temperature optical spectroscopy of [FeII(tame)2]Cl2⋅MeOH is consistent with this change in electronic ground state. These experimental results confirm the spin activity predicted for [FeII(tame)2]2+ during its de novo artificial evolution design as a spin‐crossover complex [Chem. Inf. Model. 2015, 55, 1844], offering the first experimental validation of a functional transition‐metal complex predicted by such in silico molecular design methods. Additional quantum chemical calculations offer, together with the crystal structure analysis, insight into the role of spin‐passive structural components. A thermodynamic analysis based on an Ising‐like mean field model (Slichter–Drickammer approximation) provides estimates of the enthalpy, entropy and cooperativity of the crossover between the high and low spin states.
Phosphine/Sulfoxide‐Supported Carbon(0) Complex
Authors: Lozano González Mariana , Bousquet Laura , Hameury Sophie , Alvarez Toledano Cecilio , Saffon‐Merceron Nathalie , Branchadell Vicenç , Maerten Eddy , Baceiredo Antoine 
Published: January 2018

AbstractA new carbon(0) complex 2 with two different L ligands, a phosphine and a sulfoxide, was synthesized and fully characterized. This new type of carbone exhibits excellent coordination ability, in contrast to the related phosphine/sulfide‐supported carbon(0) complexes. Several organometallic complexes were isolated and, of special interest, the νav(CO) value of RhI‐dicarbonyl complex indicates that 2 has a donor capability superior to classical NHCs.
Supramolecular Recognition of Three Way Junction DNA by a Cationic Calix[3]carbazole
Authors: Yang Zhaozheng , Chen Yan , Li Gang , Tian Zhangmin , Zhao Liang , Wu Xi , Ma Qi , Liu Mingzhe , Yang Peng 
Published: January 2018

AbstractDNA three‐way junctions (TWJ‐DNA) are intermediate structures in DNA replication and/or recombination. They play very important roles in biological processes, but more subtle functions are still unknown due partially to the lack of a fluorescent ligand. In this study, a cationic calix[3]carbazole (2) has been synthesized and its properties of interacting with TWJ‐DNA have been evaluated by UV/Vis and fluorescence spectroscopy, circular dichroism (CD), gel electrophoresis, and1H NMR studies. The results show that2binds to the central hydrophobic cavity of TWJ‐DNA. Moreover, it could selectively bind to TWJ‐DNA over duplex and quadruplex DNA. Furthermore,2possesses the capability of serving as the TWJ‐DNA probe as its trap‐II excimer emission is turned on by TWJ‐DNA.
A Saturn‐Like Complex Composed of Macrocyclic Oligothiophene and C60 Fullerene: Structure, Stability, and Photophysical Properties in Solution and the Solid State
Authors: Shimizu Hideyuki , Park Kyu Hyung , Otani Hiroyuki , Aoyagi Shinobu , Nishinaga Tohru , Aso Yoshio , Kim Dongho , Iyoda Masahiko 
Published: January 2018

AbstractA Saturn‐like 1:1 complex composed of macrocyclic oligothiophene E‐8T7A and C60 fullerene (C60) was synthesized to investigate the interaction between macrocyclic oligothiophenes and C60 in solution and the solid state. Because the Saturn‐like 1:1 complex E‐8T7A⋅C60 is mainly stabilized by van der Waals interactions between C60 and the sulfur atoms of the E‐8T7A macrocycle, C60 is rather weakly incorporated inside the macro‐ring in solution. However, in the solid state the Saturn‐like 1:1 complex preferentially formed single crystals or nanostructured polymorphs. Interestingly, X‐ray analysis and theoretical calculations exhibited hindered rotation of C60 in the Saturn‐like complex due to interactions between C60 and the sulfur atoms. Furthermore, the photoinduced charge transfer (CT) interaction between E‐8T7A and C60 in solution was investigated by using femtosecond transient absorption (TA) spectroscopy. The ultrafast TA spectral changes in the photoinduced absorption bands were attributed to the CT process in the Saturn‐like structure.
Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions
Authors: Sartzi Harikleia , Long De‐Liang , Sproules Stephen , Cronin Leroy , Miras Haralampos N. 
Published: January 2018

AbstractMixed valence/metal polyoxometalate (POM) clusters are one of the most interesting host species because they show the ability to incorporate a wide range of heteroatoms of various charges and geometries. We report herein the incorporation of pyramidal EO32− heteroanions (E=PH, S, Se, Te) that are responsible not only for directing the templated assembly of a family of mixed‐metal POMs but also for the symmetry‐breaking of the traditional Dawson architecture and modulation of the electronic characteristics of the cluster's shell. The isolated family of POMs consists of four members: (Me2NH2)5Na2[Mo11V7O52(HPO3)]⋅MeOH⋅5 H2O (1), (NH4)7[Mo11V7O52(SO3)]⋅12 H2O (2), K7[Mo11V7O52(SeO3)] ⋅31 H2O (3), and (Me2NH2)6Na[Mo11V7O52(TeO3)]⋅15 H2O (4), and were characterized by X‐ray structural analysis, electrospray ionization mass spectrometry (ESI‐MS), thermogravimetric analysis (TGA), UV/Vis, FTIR, elemental analysis, flame atomic absorption spectroscopy (FAAS), and inductively coupled plasma optical emission spectroscopy (ICP‐OES). Cyclic voltammetry (CV) and electron paramagnetic resonance (EPR) spectroscopic studies in concert with density functional theoretical (DFT) calculations have been used to elucidate the effect of the heteroatom on the electronic properties of the cluster.
All‐in‐One: Electroactive Nanocarbon as Simultaneous Platform and Label for Single‐Step Biosensing
Authors: Cheng Zhao Xuan , Bonanni Alessandra 
Published: January 2018

AbstractWe demonstrate here that an electroactive nanocarbon material can simultaneously work as both platform and label for the detection of mycotoxins. The versatility of the material for the immobilization of biorecognition elements was combined with its ability to provide an intrinsic electrochemical signal upon reduction of the oxygen functionalities on its surface. The intensity of peak current reflects the availability of oxygen functionalities for reduction, which can be directly correlated to the specific biorecognition event. We show that the use of electroactive nanocarbon as all‐in‐one biosensing component enables sensitive quantification of Fumonisin B1 (FB1) as model mycotoxin analyte, but it can be easily implemented to develop label‐free, cost‐effective and fast bioanalytical devices for universal biosensing.
Direct Catalytic Asymmetric Aldol Reaction of Thioamide with an α‐Vinyl Appendage
Authors: Cui Jin , Ohtsuki Akimichi , Watanabe Takumi , Kumagai Naoya , Shibasaki Masakatsu 
Published: January 2018

AbstractThe direct catalytic asymmetric aldol reaction is an emerging catalytic methodology that provides atom‐economical access to functionalized chiral building blocks. Thioamides are useful aldol donors due to their high‐fidelity chemoselective enolization and divergent post‐aldol transformations. Herein we describe the incorporation of an α‐vinyl appendage on a thioamide, which expands the utility of aldol adducts for natural product synthesis. This vinylated thioamide was not accommodated under the previously identified catalyst settings, but the newly developed catalytic conditions furnished aldol products containing the pendant vinyl group.
Enantiomeric resolution and modeling of DL‐alanine‐DL‐tryptophan dipeptide on amylose stationary phase
Authors: Ali Imran , Khattab Raffat A. , Alothman Zeid A. , Badjah Ahmad Yacine , Alwarthan Abdulrahman 
Published: January 2018

AbstractThe enantiomeric resolution of DL‐alanine‐DL‐tryptophan dipeptide is described on amylose stationary phase. The eluent used was CH3OH─CH3COONH4 (10mM)─CH3CN (50: 40, 10) at 0.8‐mL/min flow, 230‐nm detection, 25‐minute run time, and 25°C ± 1°C temperature. The chiral phase was amylose [AmyCoat RP (15 cm × 0.46 cm × 5 micron)]. The magnitudes of the retention factors (k) were 2.71, 3.52, 5.11, and 7.75. The magnitudes of separation factor (α) were 1.19, 1.57, and 1.51 while the resolution factors (Rs) were 3.25, 14.84, and 15.76. The limits of detection and quantitation were of 2.5 to 5.4 and 12.8 to 27.5 μg/mL. The enantiomeric resolution is controlled by hydrogen, hydrophobic, π‐π, steric, etc interactions. The elution order of the enantiomer was supported by the modeling data. The described method is fast, reproducible, precise, and selective, which can be used successfully for evaluating the enantiomers of the reported dipeptide.
Power‐to‐Liquids as Renewable Fuel Option for Aviation: A Review
Authors: Schmidt Patrick , Batteiger Valentin , Roth Arne , Weindorf Werner , Raksha Tetyana 
Published: January 2018

AbstractSevere reductions in the greenhouse gas intensity of aviation fuels are required to get a growing aviation sector on a flightpath compliant with the Paris Climate Agreement. Introducing renewable energy into aviation is challenging. The power‐to‐liquid (PtL) pathway uses renewable electricity, CO2, and water to synthesize a sustainable alternative fuel that chemically resembles conventional jet fuel. The state‐of‐art of key technologies for PtL fuel production as well as the environmental and techno‐economic performance of the resulting fuel in comparison with fossil and biomass‐derived jet fuel are reviewed.
Estragol aus Estragon
Authors: Prasse Agneta , Zeller Klaus‐Peter , Siehl Hans‐Ullrich , Berger Stefan , Sicker Dieter 
Published: January 2018

ZusammenfassungEstragol ist ein in vielen Pflanzen aus L‐Phenylalanin gebildetes Phenylpropanoid. Es kommt auch im ätherischen Öl des Französischen Estragons vor, aus dem es destillativ abgetrennt wurde. Estragon zählt neben Schnittlauch, Petersilie und Kerbel zu den vier Fines Herbes der französischen Haute Cuisine. Eine Aufnahme von Estragol in Gewürzmengen ist harmlos (dazu Rezepte), eine Überdosierung sollte vermieden werden. Estragol wurde 1892 das erste Mal als Naturstoff in Estragonöl beschrieben. Im Basischen isomerisiert Estragol zum konstitutionsisomeren trans‐Anethol. Die erste Synthese gelang 1904 über eine Wurtz‐Fittig‐Reaktion aus Allylbromid, 4‐Bromanisol und Magnesium. Estragol ist ein Paradebeispiel für spektroskopische Interpretationen. Dazu werden alle Spektren präsentiert. Dieser Beitrag setzt die Reihe zur Isolierung und Spektroskopie von Naturstoffen fort und basiert auf einer Bachelorarbeit. Er ergänzt die Kapitel des Buchs “Classics in Spectroscopy” von S. Berger und D. Sicker (Wiley‐VCH 2009).
L'impartition des activités logistiques dans le secteur de la santé: les leçons d'une expérience canadienne
Authors: Beaulieu Martin , Roy Jacques , Landry Sylvain 
Published: January 2018

AbstractLogistics activities are seen by many healthcare organizations as an opportunity for financial savings. The level of logistics complexity in these organizations may explain the challenges they face in applying solutions common in other industries. This case study of a medical‐supply distribution outsourcing initiative to a logistics services provider by a group of hospitals in a region of Canada helps elucidate this complexity. The objective of this article is to identify the dissonances between various points of view in order to articulate lessons for managers while taking into account the specifics of the healthcare sector. By examining information from several sources, this study shows the necessity of: 1) setting objectives and managing expectations in order to maintain the interest and participation of stakeholders throughout the project; 2) updating internal logistics processes prior to outsourcing; 3) carefully considering a gradual transition phase by ensuring short‐term benefits for both partners; 4) requiring problem‐solving skills as a selection criterion for the logistics services provider to ensure continuous improvement in the performance of the outsourced activity; and 5) developing a governance accountability framework to support problem solving between all parties involved. Copyright © 2018 ASAC. Published by John Wiley & Sons, Ltd.
Simulation study of sweetening and dehydration of natural gas stream using MEG solution
Authors: Alnili Firas , Barifcani Ahmed 
Published: January 2018

AbstractNatural gas is currently an important and popular fossil fuel and will likely continue to be in the future. In addition, natural gas can be considered as a source of hydrocarbon for petrochemical industries. Despite the fact that natural gas is mostly considered a “clean” fuel compared to other fossil fuels, the natural gas found in reservoir deposits is not necessarily “clean” and free of impurities. Natural gas consists primarily of methane, but it also contains considerable amounts of light and heavier hydrocarbons as well as contaminating compounds of CO2, N2, H2S, and other impurities. These impurities are undesirable compounds and cause several technical problems such as corrosion and environment pollution. However, many natural gas streams in different areas contain huge quantities of H2S and CO2. Many technologies can be used to purify the natural gas from acid gases. These technologies include Amine absorption, the adsorption process, cryogenic processes, and membranes. Therefore, this study aims to simulate the gas sweetening process by using the Aspen HYSYS V.7.3 program. Moreover, in this simulation work, MEG (Mono Ethylene Glycol) was selected as an absorbent for the gas sweetening process: it achieved high acid gas removal and reduced the water content from a stream of natural gas. In addition, the simulation work also achieved process optimization using several MEG concentrations and temperatures. It also investigated the effect of MEG concentrations and the inlet temperature of MEG on the regeneration reboiler temperature and duty.
Histological scoring of immune and stromal features in breast and axillary lymph nodes is prognostic for distant metastasis in lymph node‐positive breast cancers
Authors: Grigoriadis Anita , Gazinska Patrycja , Pai Trupti , Irhsad Sheeba , Wu Yin , Millis Rosemary , Naidoo Kalnisha , Owen Julie , Gillett Cheryl E , Tutt Andrew , Coolen Anthonius CC , Pinder Sarah E 
Published: January 2018

AbstractThe prognostic importance of lymph node (LN) status and tumour‐infiltrating lymphocytes (TILs), is well established, particularly TILs in triple negative breast cancers (TNBCs). So far, few studies have interrogated changes in involved and uninvolved LNs and evaluated if their morphological patterns add valuable information for the prediction of disease progression in breast cancer. In a cohort of 309 patients enriched for TNBCs (170/309), we histologically characterised immune and stromal features in primary tumours and associated involved and uninvolved axillary LNs on routine haematoxylin and eosin stained sections. Of the 309 patients, 143 had LN‐positive disease. Twenty‐five histopathological features were assessed, including the degree of TIL presence, quantitative and qualitative assessment of germinal centres (GCs) and sinus histiocytosis. Multivariate and cross‐validated proportional hazard regression analyses were used to identify optimal covariate sets for prediction of distant metastasis‐free survival (DMFS). The degree of intratumoural and peritumoural immune infiltrate was associated with architectural changes in both uninvolved and involved LNs. By including clinicopathological characteristics as well as tumour and LN histopathological features in L2‐regularised proportional hazard models, the prediction of 5‐year DMFS was improved by 3–15% over the baseline in all cancers and in TNBCs. In LN‐positive cancers, the combination of Salgado's classification, lymphocytic lobulitis, size and number of GCs in the uninvolved LNs and location of GCs in the involved LNs carried significant prognostic information. From these features, a multivariate cross‐validation‐stable risk signature was constructed, which identified low‐risk groups within both LN‐positive breast cancers and the LN‐positive TNBCs group with a 10‐year DMFS probability of 78 and 87%, respectively. This study illustrates that, by incorporating histopathological patterns of involved and uninvolved LNs combined with primary tumour immune and stromal features, the prediction of developing distant metastasis in LN‐positive breast cancers can be estimated more accurately.