bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Efficient Synthesis of Porphyrins with Different meso Substituents that Avoids Scrambling in Aqueous Media
Authors: Nowak‐Król Agnieszka , Plamont Rémi , Canard Gabriel , Edzang Judicaelle Andeme , Gryko Daniel T. , Balaban Teodor Silviu 
Published: November 2014

AbstractWe have developed new conditions that afford regioisomerically pure trans‐A2B2‐, A3B‐, and trans‐AB2C‐porphyrins bearing aryl and arylethynyl substituents. The porphyrins were prepared by the acid‐catalyzed condensation of dipyrromethanes with aldehydes followed by oxidation with p‐chloranil or 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ). Optimal conditions for the condensation were identified after examining various reaction parameters such as solvent composition, acid concentration, and reaction time. The conditions identified (for aromatic aldehydes: EtOH/H2O 4:1, [DPM]=4 mM, [aldehyde]=4 mM, [HCl]=38 mM, 16 h; for arylethynyl aldehydes: THF/H2O 2:1, [DPM]=13 mM, [aldehyde]=13 mM, [HCl]=150 mM, 3 h) resulted in the formation of porphyrins in yields of 9–38 % without detectable scrambling. This synthesis is compatible with diverse functionalities such as ester or nitrile. In total, 20 new trans‐A2B2‐, A3B‐, and trans‐AB2C‐porphyrins were prepared. The scope and limitations of the two sets of reaction conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in higher yields than by any other methodology and by using environmentally benign and nonhazardous chemicals.
Synthesis, Structural Characterization, and Physical Properties of Cs2Ga2S5, and Redetermination of the Crystal Structure of Cs2S6
Authors: Friedrich Daniel , Pielnhofer Florian , Schlosser Marc , Weihrich Richard , Pfitzner Arno 
Published: November 2014

AbstractThe reaction of CsN3with GaS and S at elevated temperatures results in Cs2Ga2S5. Its crystal structure was determined from single‐crystal X‐ray diffraction data. The colorless solid crystallizes in space groupC2/c(no. 15) withV=1073.3(4) Å3andZ=4. Cs2Ga2S5is the first compound that features one‐dimensional chains${{{\hfill 1\atop \hfill \infty }}}$[Ga2S3(S2)2−] of edge‐ and corner‐sharing GaS4tetrahedra. The vibrational band of the S22−units at 493 cm−1was revealed by Raman spectroscopy. Cs2Ga2S5has a wide bandgap of about 3.26 eV. The thermal decomposition of CsN3yields elemental Cs, which reacts with sulfur to provide Cs2S6as an intermediate product. The crystal structure of Cs2S6was redetermined from selected single crystals. The red compound crystallizes in space group${P\bar 1}$withV=488.99(8) Å3andZ=2. Cs2S6consists of S62−polysulfide chains and two Cs positions with coordination numbers of 10 and 11, respectively. Results of DFT calculations on Cs2Ga2S5are in good agreement with the experimental crystal structure and Raman data. The analysis of the chemical bonding behavior revealed completely ionic bonds for Cs, whereas GaS and SS form polarized and fully covalent bonds, respectively. HOMO and LUMO are centered at the S2units.
Chiral Calcium–BINOL Phosphate Catalyzed Diastereo‐ and Enantioselective Synthesis of syn‐1,2‐Disubstituted 1,2‐Diamines: Scope and Mechanistic Studies
Authors: Lalli Claudia , Dumoulin Audrey , Lebée Clément , Drouet Fleur , Guérineau Vincent , Touboul David , Gandon Vincent , Zhu Jieping , Masson Géraldine 
Published: November 2014

AbstractA highly enantioselective, chiral, Lewis acid calcium–bis(phosphate) complex, Ca[3 a]n, which catalyzes the electrophilic amination of enamides with azodicarboxylate derivatives 2 to provide versatile chiral 1,2‐hydrazinoimines 4 is disclosed. The reaction gives an easy entry to optically active syn‐1,2‐disubstituted 1,2‐diamines 6 in high yields with excellent enantioselectivities, after a one‐pot reduction of the intermediate 1,2‐hydrazinoimines 4. The geometry and nature of the N‐substituent of the enamide affect dramatically both the reactivity and the enantioselectivity. Although the calcium–bis(phosphate) complex was a uniquely effective catalyst, the exact nature of the active catalytic species remains unclear. NMR spectroscopy and MS analysis of the various calcium complexes Ca[3]n reveals that the catalysts exist in various oligomer forms. The present mechanistic study, which includes nonlinear effects and kinetic measurements, constitutes a first step in understanding these calcium–bis(phosphate) complex catalysts. DFT calculations were carried out to explore the mechanism and the origin of the enantioselectivity with the Ca[3]n catalysts.
Synthesis and Characterization of ortho‐Thio‐Functionalized Triarylmethyl Palladium Complexes
Authors: Schöler Stephan , Merz Klaus , Puls Arik , Winter Manuela , Dyker Gerald 
Published: November 2014

AbstractA series of triarylmethyl palladium complexes with ortho coordination sites were synthesized. Thereby, the palladium atom exhibits various inter‐ and intramolecular binding modes towards the organic ligand. Further, the first crystallographically proven, exclusively σ‐coordinated triarylmethyl palladium complexes, stabilized by ortho‐thio‐substituents, were discovered. The NMR spectra of the palladium complexes indicate temperature‐dependent dynamic behavior.
Voltammetric Determination of Nitrofurantoin at a Mercury Meniscus Modified Silver Solid Amalgam Electrode
Authors: Krejčová Zuzana , Barek Jiří , Vyskočil Vlastimil 
Published: November 2014

AbstractElectrochemical behavior of nitrofurantoin (NF) was studied by direct current voltammetry (DCV), differential pulse voltammetry (DPV), and cyclic voltammetry (CV) using a mercury meniscus modified silver solid amalgam electrode (m‐AgSAE). Voltammetric behavior of NF was studied in cathodic region of potentials in dependence on pH. pH 7.0 was selected as an optimal medium for the determination of NF by both DCV and DPV, with the optimal methanolwater volume ratio of 1 : 9. In order to reduce the negative influence of electrode passivation, the suitable regeneration potentials were found (0 mV and −900 mV). The optimal conditions were found for the determination of NF in concentration ranges from 6×10−6 mol L−1 to 1×10−4 mol L−1 using DCV technique, and from 2×10−7 mol L−1 to 1×10−4 mol L−1 using DPV technique, both in the medium of methanolBritton–Robinson buffer pH 7.0 (1 : 9). The attained limit of quantification (LOQ) of NF was 1.6×10−6 mol L−1 for DCV and 8.1×10−8 mol L−1 for DPV. The practical applicability of the newly developed DPV method was verified by direct determination of NF in model samples of drinking and river water, with LOQs 2.2×10−7 mol L−1 and 2.5×10−7 mol L−1, respectively.
Analysis of Evaluation Indicators for Furrow Irrigation Using Opportunity Time
Authors: Lalehzari REZA , Ansari Samani FARIDE , Boroomand‐nasab SAEED 
Published: November 2014

AbstractEvaluation procedures have been developed for effective design and management of irrigation systems. Furrow irrigation is one of the main types of applying water in the field. In the present study, a new procedure for field evaluation of water distribution in furrow irrigation is proposed. For this purpose, application efficiency (Ea), water requirement efficiency (Er), deep percolation (DP) and tail water ratio (TWR) have been introduced, based on the average of dimensionless infiltrated depth values in the four data groups. The relationships between coefficient of uniformity CU and distribution uniformity DU have been described by opportunity time values of each quarter and using the linear equation instead of the infiltration function. The proposed procedure was compared to existing methods by nine irrigation scenarios including three furrow length and three inflow rates. The results show that the evaluation indicators of furrow irrigation calculated with non‐dimensional parameters depend on opportunity time and new coefficients of the linear infiltration equation. Also, there was no observed significant difference on the suggested indice values and classical performance indicators. Copyright © 2015 John Wiley & Sons, Ltd.
The Preparation of Slag Fiber and Its Application in Microwave Absorption
Authors: Wang To‐Mai , Ting Tzu‐Hao , Yeh Feng‐Mei 
Published: November 2014

AbstractIn this research, the slag fibers coming from water‐quenched slags by using thermal plasma technology were successfully prepared and introduced into epoxy resin to be microwave absorber. The fiber‐blowing equipment for manufacturing slag fibers through controlling the nozzle angle and vertical distance from the nozzle to the melt outlet was also studied. The spectroscopic characterization of the formation processes of slag fiber was studied by using X‐ray diffraction (XRD), inductively‐coupled plasma (ICP), differential thermal analysis (DTA) and scanning electron microscopy (SEM). Microwave absorbing properties of the slag fibers and thermal plastic resin were investigated by measuring reflection loss in the 2–18 and 18–40 GHz microwave frequency range using the free space method. It was found that the composite specimens of slag fiber and thermal plastic resin had the best microwave absorption due to the reflection losses between from −4 to −8 dB and from −11 to −17 dB at frequencies between 2–18 and 18–40 GHz.
An Evaluation of Traditional Seed Conservation Methods in Rural Malawi
Authors: Mngoli Mtisunge B. , Mkwambisi David D. , Fraser Evan D. G. 
Published: November 2014

AbstractIndigenous traditional methods of saving and storing seeds are often seen as viable alternatives to purchasing hybridised seeds for small‐scale farmers across the developing world. Nevertheless, little research has been conducted on which particular seed saving methods are most effective. Therefore, the purpose of this paper is to both document and test the efficacy of different traditional seed saving methods practiced by small‐scale farmers in rural Malawi. Methods involved conducting both a survey and semi‐structured interview with 40 small‐scale farmers all of whom practiced different forms of traditional seed saving. A representative sample of sorghum and maize seeds were collected from each of these farms and grown in laboratory conditions to test the efficacy and germination rates of seeds stored using different practices. The results revealed that farmers used a wide range of indigenous seed saving techniques that include burning animal manure and covering seeds with the resulting ash to being stored in cloth bags or ceramic containers. The impact of these methods range considerably. Some methods, such as smoking the seeds over the cooking fire, proved ineffective, and germination rates were very low in seeds treated in this way. However, other methods, such as grinding up a local leaf into a powder and covering the seeds with the powder, were as effective as treating the seeds with commercial fungicides. Furthermore, these indigenous methods cost a fraction of the amount of commercially available methods' cost and are also much less expensive than buying seeds annually. The implication of this research is that it is important for researchers to test the efficacy of traditional seed saving methods as a way of establishing best practices and developing appropriate agricultural management practices that will help farmers alleviate poverty. Copyright © 2014 John Wiley & Sons, Ltd.
The Detection of Deception Within Investigative Contexts: Key Challenges and Core Issues
Authors: Ioannou Maria , Hammond Laura 
Published: November 2014

AbstractA large and continually growing body of research has explored the ways in which deception might be detected. The area is developing rapidly, opening up new avenues of study. This special issue of the Journal of Investigative Psychology and Offender Profiling brings together an exciting array of papers on the detection of deception within investigative contexts, examining a wide range of issues including the efficacy of different interviewing techniques, the reliability of statement veracity assessment, factors influencing ability to detect deception and the need for applied research and ecologically valid studies. This examination of the key challenges and core issues surrounding the detection of deception within the criminal justice domain helps move the field forward, providing powerful results that have potentially far‐reaching impacts. These are considered in detail throughout the following discussion. Copyright © 2014 John Wiley & Sons, Ltd.
Efficient Regioselective Ring Opening of Activated Aziridine‐2‐Carboxylates with [18F]Fluoride
Authors: Schjoeth-Eskesen Christina , Hansen Paul Robert , Kjaer Andreas , Gillings Nic 
Published: November 2014

AbstractAziridines can undergo a range of ring‐opening reactions with nucleophiles. The regio‐ and stereochemistry of the products depend on the substituents on the aziridine. Aziridine ring‐opening reactions have rarely been used in radiosynthesis. Herein we report the ring opening of activated aziridine‐2‐carboxylates with [18F]fluoride. The aziridine was activated for nucleophilic attack by substitution of various groups on the aziridine nitrogen atom. Fluorine‐18 radiolabelling was followed by ester hydrolysis and removal of the activation group. Totally regioselective ring opening and subsequent deprotection was achieved with tert‐butyloxycarbonyl‐ and carboxybenzyl‐activated aziridines to give α‐[18F]fluoro‐β‐alanine in good radiochemical yield.
Regioisomer‐Free C4h β‐Tetrakis(tert‐butyl)metallo‐phthalocyanines: Regioselective Synthesis and Spectral Investigations
Authors: Iida Norihito , Tanaka Kenta , Tokunaga Etsuko , Takahashi Hiromi , Shibata Norio 
Published: November 2014

AbstractMetal β‐tetrakis(tert‐butyl)phthalocyanines are the most commonly used phthalocyanines due to their high solubility, stability, and accessibility. They are commonly used as a mixture of four regioisomers, which arise due to the tert‐butyl substituent on the β‐position, and to the best of our knowledge, their regioselective synthesis has yet to be reported. Herein, the C4h‐selective synthesis of β‐tetrakis(tert‐butyl)metallophthalocyanines is disclosed. Using tetramerization of α‐trialkylsilyl phthalonitriles with metal salts following acid‐mediated desilylation, the desired metallophthalocyanines were obtained in good yields. Upon investigation of regioisomer‐free zinc β‐tetrakis(tert‐butyl)phthalocyanine using spectroscopy, the C4h single isomer described here was found to be distinct in the solid state to zinc β‐tetrakis(tert‐butyl)phthalocyanine obtained by a conventional method.
Decreased domain size and improved crystallinity by adjusting solvent–polymer interaction parameters in all‐polymer solar cells
Authors: Zhou Ke , Liu Jiangang , Li Mingguang , Yu Xinhong , Xing Rubo , Han Yanchun 
Published: November 2014

ABSTRACTWe have investigated the effect of solvent–polymer interaction on the morphology, crystallinity, and device performance of poly‐(3‐hexylthiophene) (P3HT) and poly{2,7‐(9,9‐didodecyl‐fluorene)‐alt‐5,5‐[4′,7′‐bis(2‐thienyl)‐2′,1′,3′‐benzothia‐diaole]} (PF12TBT) blend system. 3‐Hexylthiophene (3‐HT), which had the similar structural units with both donor and acceptor materials, was chosen as the solvent additive to be added into the main solvent chlorobenzene (CB), to adjust the solvent–polymer interaction. With the 3‐HT percentage increasing from 5 to 30% in CB solution, the solvent–polymer interaction between polymer and solvent molecules decreased slightly according to the calculated solubility parameters (δ) and interaction parameters (χ12). As a result, nanoscale phase‐separated and interconnected morphology with decreased domain size of both donor and acceptor was formed. Meanwhile, the order of P3HT molecule was enhanced which resulted from the extended film drying time and increased molecular planarity after incorporation of 3‐HT. The power conversion efficiency (PCE) had a gradual improvement to 1.08% as the 3‐HT percentage reached 10%, which can be attributed to the enhanced short‐circuit current (Jsc) and fill factor (FF). However, when the 3‐HT percentage exceeded 20%, the decreased Jsc and FF ultimately decreased the PCE. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 288–296
Surgical Treatment of Incidental Gallbladder Cancer Discovered During or Following Laparoscopic Cholecystectomy
Authors: Tian Yuan‐Hu , Ji Xu , Liu Bo , Yang Guang‐Yun , Meng Xiang‐Fei , Xia Hong‐Tian , Wang Jing , Huang Zhi‐Qiang , Dong Jia‐Hong 
Published: November 2014

AbstractBackgroundThe optimal surgical management of patients with incidental gallbladder cancer (IGBC) and their long‐term survival remains unclear.ObjectiveThe purpose of this study was to examine the long‐term prognosis of patients with IGBC diagnosed during or after LC.MethodsBetween January 2002 and January 2012, a total of 7,582 consecutive patients underwent LC for presumed gallbladder benign disease in the Chinese PLA General Hospital, China. Among them, 69 patients (0.91 %) were diagnosed to have IGBC. Their medical records, imaging data, surgery records, pathological findings, and survival data were retrospectively reviewed.ResultsMedian age was 61 years (range: 34–83). After a median follow‐up period of 61 months, the 1‐, 3‐, and 5‐year survival rates of patients were 89.9, 78.3, and 76.8 %, respectively. The 5‐year survival rates of patients with T1a, T1b, T2, and T3 stages were 95.5, 93.8, 69.2, and 44.4 %, respectively. The 5‐year survival rates in simple LC (n = 45), converted to open extended cholecystectomy (n = 16), and radical second resection (n = 8) groups were 91.1, 37.5, and 75.0 %, respectively. Local port‐site tumor recurrence was identified in one patient. Prognostic factors including depth of invasion, lymph node status, vascular or neural invasion, tumor differentiation, extent of resection, bile spillage, and type of surgery were statistically significant (p < 0.05).ConclusionsSimple LC is appropriate for T1a patients with clear margin and unbroken gallbladder, whereas extended radical resection is recommended for patients with T1b or more advanced IGBC. An intact surgical specimen and the use of plastic retrieval bags are important to reduce the risk of port‐site recurrences and disease relapse. Early diagnosis, meticulous perioperative assessment, and precise surgery are essential factors to obtain good results in IGBC treatment.
Principles and practice of lipidomics
Authors: Vaz Frédéric M. , Pras‐Raves Mia , Bootsma Albert H. , van Kampen Antoine H. C. 
Published: November 2014

AbstractThe technical advances in mass spectrometry, particularly the development of (ultra)‐high‐resolution/mass accuracy measurement capabilities in combination with refinement of soft ionization techniques, have increased the application and success of lipidomics to answer biological questions in relation to lipid metabolism. Together with other omics technologies, lipidomics has become an important tool to practice systems biology as lipids comprise a very significant part of the metabolome and play pleiotropic roles in cellular functions. As an increasing number of disorders are linked to lipid metabolism, lipidomics is used to search for biomarkers, understand disease mechanism and follow the efficacy of therapeutic options. This review provides a first introduction to the major methodological strategies currently used for mass spectrometry‐based lipidomics and associated data pre‐processing and analysis.
A Genetic Lung Cancer Susceptibility Test may have a Positive Effect on Smoking Cessation
Authors: Kammin Tammy , Fenton Andrew K. , Thirlaway Kathryn 
Published: November 2014

AbstractSmoking increases the risk of developing lung cancer. Genetic loci have been identified which could form the basis of a lung cancer susceptibility test; but little is known whether such a test would interest or motivate those trying to quit smoking. To address this, we investigated the attitudes of people trying to quit smoking towards genetic susceptibility testing for lung cancer. Participant's attitudes to topics associated with lung cancer susceptibility testing were assessed; were they interested in genetic testing? What impact would a hypothetical high‐ or low‐ risk result have on smoking cessation? 680 self‐completion questionnaires were given to individuals attending National Health Service stop smoking clinics in three different areas of the United Kingdom between 2011 and 2012. 139 questionnaires were returned, giving a 20 % response rate. Participants expressed an interest in a genetic susceptibility test for lung cancer and almost all reported that a high‐risk result would increase their motivation to stop smoking. However, many participants had a neutral attitude towards a low‐risk result. Most participants agreed their smoking habit could lead to lung cancer. Lung cancer susceptibility testing may be a useful incentive to help people quit smoking. This study suggests the need for genetic services to work with smoking cessation teams if routine testing becomes available in the future.
EPA and DHA Exposure Alters the Inflammatory Response but not the Surface Expression of Toll‐like Receptor 4 in Macrophages
Authors: Honda Kaori L. , Lamon‐Fava Stefania , Matthan Nirupa R. , Wu Dayong , Lichtenstein Alice H. 
Published: November 2014

AbstractDietary intake of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) and their respective enrichment in cell membranes have been negatively associated with atherosclerotic lesion development. This effect may be mediated, in part, by dampened inflammatory response of macrophages triggered by toll‐like receptor 4 (TLR4) activation. This study investigated the influence of membrane fatty acid profile on TLR4‐mediated inflammation in RAW 264.7 macrophages. Cells pretreated with myristic acid (MA), EPA, DHA or vehicle control for 24 h were stimulated with ultra‐pure LPS, a specific TLR4 agonist, for 6 or 24 h, corresponding to early and late stages of TNFα and IL‐6 protein induction. Treatment significantly increased cell membrane MA, EPA, and DHA by 4.5‐, 20.6‐, and 8.9‐fold, respectively. MA significantly increased IL‐6 secretion 6 h post‐exposure to the fatty acid, but did not change TNFα secretion in response to any other treatment condition. EPA and DHA significantly reduced TNFα secretion by 36 and 41 %, respectively, in cells stimulated for 24 h but not 6 h. In contrast, EPA and DHA significantly reduced IL‐6 secretion at both 6 h (67 and 72 %, respectively) and 24 h (69 and 72 %, respectively). MA or DHA treatment had no significant effect compared to vehicle on factors influencing cellular LPS recognition, including LPS‐cell association, and cell surface expression of TLR4, TLR4‐MD2 complex, and CD14. These data suggest that membrane fatty acid profiles influence the TLR4‐mediated inflammatory response in macrophages, via mechanisms that occur downstream of TLR4 receptor activation.