bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dynamic intermediate ocean circulation in the North Atlantic during Heinrich Stadial 1: A radiocarbon and neodymium isotope perspective
Authors: Wilson David J. , Crocket Kirsty C. , van de Flierdt Tina , Robinson Laura F. , Adkins Jess F. 
Published: September 2014

AbstractThe last deglaciation was characterized by a series of millennial‐scale climate events that have been linked to deep ocean variability. While often implied in interpretations, few direct constraints exist on circulation changes at mid‐depths. Here we provide new constraints on the variability of deglacial mid‐depth circulation using combined radiocarbon and neodymium isotopes in 24 North Atlantic deep‐sea corals. Their aragonite skeletons have been dated by uranium‐series, providing absolute ages and the resolution to record centennial‐scale changes, while transects spanning the lifetime of a single coral allow subcentennial tracer reconstruction. Our results reveal that rapid fluctuations of water mass sourcing and radiocarbon affected the mid‐depth water column (1.7–2.5 km) on timescales of less than 100 years during the latter half of Heinrich Stadial 1. The neodymium isotopic variability (−14.5 to −11.0) ranges from the composition of the modern northern‐sourced waters towards more radiogenic compositions, suggesting the presence of a greater southern‐sourced component at some times. However, in detail, simple two‐component mixing between well‐ventilated northern‐sourced and radiocarbon‐depleted southern‐sourced water masses cannot explain all our data. Instead, corals from ~15.0 ka and ~15.8 ka may record variability between southern‐sourced intermediate waters and radiocarbon‐depleted northern‐sourced waters, unless there was a major shift in the neodymium isotopic composition of the northern end‐member. In order to explain the rapid shift towards the most depleted radiocarbon values at ~15.4 ka, we suggest a different mixing scenario involving either radiocarbon‐depleted deep water from the Greenland‐Iceland‐Norwegian Seas or a southern‐sourced deep water mass. Since these mid‐depth changes preceded the Bolling‐Allerod warming and were apparently unaccompanied by changes in the deep Atlantic, they may indicate an important role for the intermediate ocean in the early deglacial climate evolution.
Eliciting Information and Detecting Lies in Intelligence Interviewing: An Overview Of Recent Research
Authors: Vrij Aldert , Granhag Pär Anders 
Published: September 2014

SummaryTraditional police–suspect interviews differ from intelligence interviews in several important ways, and these differences merit new research activities. This article presents an overview of recent and innovative research into eliciting information and cues to deceit in intelligence interviews, and discusses research into new domains including ‘lying about intentions’, ‘undercover interviewing’, and ‘collective interviewing’. Although that research is still in its infancy, the findings reveal that truth tellers' and liars' answers can be distinguished from each other if the correct interview protocols are implemented, such as asking unexpected questions and introducing forced turn‐taking. In addition, this new research also shows that the so‐called Scharff technique is more effective for eliciting human intelligence information compared with more traditional techniques. Copyright © 2014 John Wiley & Sons, Ltd.
2013 American College of Rheumatology/European League Against Rheumatism Classification Criteria for Systemic Sclerosis Outperform the 1980 Criteria: Data From the Canadian Scleroderma Research Group
Authors: Alhajeri Hebah , Hudson Marie , Fritzler Marvin , Pope Janet , Tatibouet Solène , Markland Janet , Robinson David , Jones Niall , Khalidi Nader , Docherty Peter , Kaminska Elzbieta , Masetto Ariel , Sutton Evelyn , Mathieu Jean‐Pierre , Ligier Sophie , Grodzicky Tamara , LeClercq Sharon , Thorne Carter , Gyger Geneviève , Smith Douglas , Fortin Paul R. , Larché Maggie , Baron Murray 
Published: September 2014

ObjectiveThe goal of this study was to determine the sensitivity of the new 2013 classification criteria for systemic sclerosis (SSc; scleroderma) in an independent cohort of SSc subjects and to assess the contribution of individual items of the criteria to the overall sensitivity.MethodsSSc subjects from the Canadian Scleroderma Research Group cohort were assessed. Sensitivity was determined in several subgroups of patients. In patients without the criterion of skin thickening proximal to the metacarpophalangeal (MCP) joints, we recalculated sensitivity after removing the individual criterion.ResultsA total of 724 SSc patients were included. Most were women (86%), mean age was 55.8 years, mean disease duration was 10.9 years, and 59% had limited cutaneous SSc (lcSSc). Overall, the sensitivity of the 2013 criteria was 98.3% compared to 88.3% for the 1980 criteria. This pattern was consistent among those with lcSSc (98.8% versus 85.6%), anticentromere antibodies (98.9% versus 79.8%), disease duration ≤3 years (98.7% versus 84.7%), and no skin involvement proximal to the MCP joints (97% versus 60%). In the latter subgroup, removing Raynaud's phenomenon and sclerodactyly from the criteria reduced the sensitivity to 77% and 79%, respectively. Removing both sclerodactyly and puffy fingers reduced the sensitivity to 62%.ConclusionThe 2013 SSc classification criteria classify more SSc patients than the 1980 criteria. The improvement in sensitivity is most striking in those with lcSSc, especially those without skin involvement proximal to the MCP joints. The addition of Raynaud's phenomenon and puffy fingers to the 2013 criteria accounts for important gains in sensitivity.
Investigating the Photostability of Quantum Dots at the Single‐Molecule Level
Authors: Zhao Wenfeng , Dong Suli , Sun Lichun , Wang Qi , Gai Hongwei 
Published: September 2014

AbstractQuantum dots (QDs) have shown great potential to provide spatial, temporal, and structural information for biological systems. However, blinking, photobleaching, and spectral blueshift are adverse effects on their practical applications in biomedical research. An investigation of the effects of six reducing agents including cysteine (Cys), 1,4‐dithiothreitol (DTT), ethyl gallate (EG), L‐glutathione (GSH), mercaptoacetic acid (MAA), and thiourea (TU) on the photostability of single QDs was studied. Our experiments demonstrate that both DTT and EG effectively inhibit blinking, photobleaching, and spectral blueshift. GSH molecules block blinking and photobleaching of QDs. The other reagents, Cys, MAA, and TU, only have the ability to counteract blinking. Possible explanations are given on the basis of research evidence. The results suggest possibilities for significant improvements in QDs for biological applications by adjusting the environmental conditions.
Ursolic acid induced apoptotic cell death following activation of caspases in isolated human melanoma cells
Authors: Mahmoudi Mahmoud , Rabe Shahrzad Zamani Taghizadeh , Balali‐Mood Mahdi , Karimi Gholamreza , Tabasi Nafiseh , Riahi‐Zanjani Bamdad 
Published: September 2014

AbstractUrsolic acid (UA) is plentifully present in fruits, foods, and medicinal plants, and has anti‐cancer activity on many cancer cell lines. However, the effects of UA on some melanoma cells and the mechanisms of action have not been reported. The effect of UA on isolated human melanoma and fibroblast cell lines has been investigated using the MTT assay, and cell death was determined using Annexin‐V/PI staining. To explore whether the activation of caspases was required for apoptosis induction, cells were treated with pan‐caspase inhibitor and UA. Changes in apoptosis pattern were analyzed by flow cytometry. Activation of caspases was detected by western blot analysis. A significant concentration‐dependent suppression of cell proliferation was seen after 24 and 48 h in the presence of UA. Apoptosis was considerably increased by UA, indicated by enhancement of an Annexin‐V positive population and a sub‐G1 peak. UA induced proteolytic processing of caspase‐3. The results confirm the anti‐cancer properties of UA on cultured human melanoma cells, possibly mediated through the induction of apoptosis following activation of caspases.
Functional Redundancy of Microbial Anodes fed by Domestic Wastewater
Authors: Koch Christin , Popiel Dominika , Harnisch Falk 
Published: September 2014

AbstractMicrobial electrochemical technologies (METs) represent a promising platform for sustainable wastewater treatment. Thereby, METs may not only allow energy savings by reducing the need for aeration, but may even aim at providing an additional energy gain, for example, as electricity in microbial fuel cells (MFCs). The key element is the anode community, in which complex wastewater constituents are broken down and extracellular electron transfer is performed. So far, most studies exploiting real domestic wastewater for METs have focused on the engineering perspective. In this study, the role of the microbial community of anodes in treating domestic wastewater was investigated. Wastewater of a primary clarifier was regularly fed to 400 mL batch reactors and the systems performance was assessed in terms of chemical oxygen demand removal, current production, and coulombic efficiency, as well as biomass formation and biomass composition. Originating from an identical source and regularly fed with identical wastewaters, microbially diverse but functionally stable electroactive anode biofilms were formed, demonstrating functional redundancy as well as flexibility.
Epimerization of Glycal Derivatives by a Cyclopentadienylruthenium Catalyst: Application to Metalloenzymatic DYKAT
Authors: Lihammar Richard , Rönnols Jerk , Widmalm Göran , Bäckvall Jan‐E. 
Published: September 2014

AbstractEpimerization of a non‐anomeric stereogenic center in carbohydrates is an important transformation in the synthesis of natural products. In this study an epimerization procedure of the allylic alcohols of glycals by cyclopentadienylruthenium catalyst 1 is presented. The epimerization of 4,6‐O‐benzylidene‐D‐glucal 4 in toluene is rapid, and an equlibrium with its D‐allal epimer 5 is established within 5 min at room temperature. Exchange rates for allal and glucal formation were determined by 1D 1H EXSY NMR experiments to be 0.055 s−1 and 0.075 s−1, respectively. For 4‐O‐benzyl‐L‐rhamnal 8 the epimerization was less rapid and four days of epimerization was required to achieve equilibration of the epimers at room temperature. The epimerization methodology was subsequently combined with acylating enzymes in a dynamic kinetic asymmetric transformation (DYKAT), giving stereoselective acylation to the desired stereoisomers 12, 13, and 15. The net effect of this process is an inversion of a stereogenic center on the glycal, and yields ranging from 71 % to 83 % of the epimer were obtained.
Distortions of π‐Coordinated Arenes with Anionic Character
Authors: Falceto Andrés , Casanova David , Alemany Pere , Alvarez Santiago 
Published: September 2014

AbstractA qualitative analysis of the distortions that operate on the π system of bridging arenes with anionic character is presented and substantiated by computational studies at the density functional B3LYP and CASSCF levels. The observed effects of bonding to two metal atoms and of the negative charge are an expansion of the arene ring due to the partial occupation of π* orbitals, an elongation or compression distortion accompanied by a loss of the equivalence of carbon‐carbon bonds due to a Jahn–Teller distortion of the arene dianions, and a ring puckering due to a second‐order Jahn–Teller distortion that may appear independently of the existence of the first‐order effect. The workings of the orbital mixing produced by these distortions have been revealed in a straightforward way by a pseudosymmetry analysis of the HOMOs of the distorted conformations. The systems studied include LiI and YIII adducts of benzene, as well as trimethylsilyl‐substituted derivatives in the former case. An analysis of the structural data of a variety of purported di‐ and tetraanionic arene ligands coordinated to transition metals in several bridging modes has reproduced the main geometrical trends found in the computational study for the benzene and trimethylsilyl‐substituted benzene dianions, allowing a classification of the variety of structural motifs found in the literature.
Translation of Dicarboxylate Structural Information to Fluorometric Optical Signals through Self‐Assembly of Guanidinium‐Tethered Oligophenylenevinylene
Authors: Noguchi Takao , Roy Bappaditya , Yoshihara Daisuke , Tsuchiya Youichi , Yamamoto Tatsuhiro , Shinkai Seiji 
Published: September 2014

AbstractAlthough self‐assembly has realized the spontaneous formation of nanoarchitectures, the nanoscopic expression of chemical structural information at the molecular level can alternatively be regarded as a tool to translate molecular structural information with high precision. We have found that a newly developed guanidinium‐tethered oligophenylenevinylene exhibits characteristic fluorescence (FL) responses toward L‐ and meso‐tartarate, wherein the different self‐assembly modes, termed J‐ or H‐type aggregation, are directed according to the molecular information encoded as the chemical structure. This morphological difference originates from the geometric anti versus gauche conformational difference between L‐ and meso‐tartarate. A similar morphological difference can be reproduced with the geometric CC bond difference between fumarate and maleate. In the present system, the dicarboxylate structural information is embodied in the inherent threshold concentration of the FL response, the signal‐to‐noise ratio, and the maximum FL wavelength. These results indicate that self‐assembly is meticulous enough to sense subtle differences in molecular information and thus demonstrate the potential ability of self‐assembly for the expression of a FL sensory system.
One‐Step Synthesis of Metal@Titania Core–Shell Materials for Visible‐Light Photocatalysis and Catalytic Reduction Reaction
Authors: Xiong Zhigang , Zhang Luhong , Zhao Xiu Song 
Published: September 2014

AbstractMetal@TiO2 composites with a core–shell structure possess multifunctional properties. The demonstrated protocols for synthesizing such materials involve multiple steps, requiring precise control over the particle uniformity of the core and shell thickness, as well as complex surface modification. A simple approach to synthesizing metal@TiO2 hybrid nanostructures remains a great challenge. Herein, we report on a one‐step method for the preparation of metal@TiO2 core–shell nanospheres, which exhibited excellent performance in photocatalytic degradation of recalcitrant organic pollutants under visible light irradiation, and in catalytic reduction of nitrophenol in water. The simple method described here represents a sustainable approach to preparing core–shell materials at low cost, involving fewer chemicals, and requiring less energy, which will make a significant contribution toward large‐scale synthesis of high‐performance hybrid materials for photocatalytic applications.
Synthesis of Highly Substituted N‐(Furan‐3‐ylmethylene)benzenesulfonamides by a Gold(I)‐Catalyzed Oxidation/1,2‐Alkynyl Migration/Cyclization Cascade
Authors: Wang Tao , Huang Long , Shi Shuai , Rudolph Matthias , Hashmi A. Stephen K. 
Published: September 2014

AbstractA variety of N‐(furan‐3‐ylmethylene)benzenesulfonamides were obtained by a gold(I)‐catalyzed cascade reaction from easily accessible starting materials. The reaction pathway involves a rarely observed 1,2‐alkynyl migration onto a gold carbenoid. This observation further enriches gold carbenoid chemistry with regard to group migration.
Design, Synthesis, and Biological Evaluation of Shikonin and Alkannin Derivatives as Potential Anticancer Agents via a Prodrug Approach
Authors: Wang Ru‐Bing , Zhou Wen , Meng Qing‐Qing , Zhang Xu , Ding Jing , Xu Yan , Song Hua‐Long , Yang Kai , Cui Jia‐Hua , Li Shao‐Shun 
Published: September 2014

AbstractTo minimize the cytotoxicity of shikonin and alkannin that arises through the generation of reactive oxygen species (ROS) and alkylation of the naphthazarin ring, two series of novel core‐scaffold‐modified shikonin and alkannin derivatives were designed. These derivatives, which differ in their configurational and positional isomerism (R‐, S‐, and 2‐ and 6‐isomers) were synthesized in high enantiomeric excess (>99 % ee). The selectivity of the dimethylated derivatives was significantly higher than the parent shikonin in vitro, but some side effects were still observed in vivo. Surprisingly, the dimethylated diacetyl derivatives with poor anticancer activity in vitro showed tumor‐inhibiting effects similar to paclitaxel without any toxicity in vivo. The anticancer activity of these derivatives is in agreement with their low ROS generation and alkylating capacity, emphasizing their potential as prodrugs. This strategy provides means to address the nonspecific cytotoxicity of naphthazarin analogues toward normal cells.
The Lineshape of the Electronic Spectrum of the Green Fluorescent Protein Chromophore, Part II: Solution Phase
Authors: Avila Ferrer Francisco J. , Davari Mehdi D. , Morozov Dmitry , Groenhof Gerrit , Santoro Fabrizio 
Published: September 2014

AbstractThe vibronic spectra of the green fluorescent protein chromophore analogues p‐hydroxybenzylidene‐2,3‐dimethylimidazolinone (HBDI) and 3,5‐tert‐butyl‐HBDI (35Bu) are similar in the vacuum, but very different in water or ethanol. To understand this difference, we have computed the vibrationally resolved solution spectra of these chromophores, using the polarizable continuum model (PCM) to account for solvent effects on the (harmonic) potential energy surfaces (PES). In agreement with experiment, we found that the vibrational progression increases with the polarity of the solvent, but we could neither reproduce the broadening, nor the large difference between the absorption spectra of HBDI and 35Bu. To account for the inhomogeneous broadening of the solution spectra, we used two approaches. In the first, we estimated the polar broadening from the solvent reorganization energy upon photo‐excitation, using the state‐specific PCM implementation. In the second, we estimated the broadening from the variance of the vertical excitation energies in molecular dynamics trajectories. Although we found good agreement for the lineshape of 35Bu in ethanol, and to a lesser extent in water, we highly underestimated the broadening for HBDI. To resolve this discrepancy, we explored the PES of HBDI in water and found that in contrast to the PCM result, the ground‐state geometry is not planar in explicit solvent. We furthermore found that nonplanar geometries enhance the intramolecular charge transfer upon excitation. Therefore, the solvent reorganization and broadening are much larger and we speculate that the much broader spectrum of HBDI in water is due to the population of nonplanar geometries.
2‐Pyridylcyanoxime–NiII Clusters with Unusual Topologies: Lone‐Pair–π Interactions and Magnetic Properties
Authors: Escuer Albert , Esteban Jordi , Mayans Júlia , Font‐Bardia Mercè 
Published: September 2014

AbstractThree new complexes derived from the reaction of the 2‐pyridylcyanoxime ligand (pyC{CN}NOH) with several non‐carboxylate nickel salts have been structural and magnetically characterized. The compounds with the formula [Ni3(MeOH)2(CF3COO)(OH)(pyC{CN}NO)4] (1), [NaNi(tfacac)3]n (2; tfacac = 1,1,1‐trifluoroacetylacetone), [Ni5(H2O)2(N3)2(pyC{CN}NO)8] (3), and [Ni3(pyC{CN}NO)5(pyC{CN}NOH)](BF4) (4) exhibit unusual topologies with a triangular {Ni3(μ3‐OH)(pyC{R′}NO)3}2+ core for 1, vertex‐shared triangles with a {Ni5(μ1,1‐N3)2(pyC{CN}NO)6}2+ core for 3, and a {Ni3(pyC{CN}NO)4}2+ core for 4. Direct‐current (DC) magnetic measurements performed in the 2–300 K temperature range reveal antiferromagnetic interactions induced by the μ3‐OR or oximato superexchange pathways and ferromagnetic interactions promoted by the azido bridges, thereby resulting in ground states S = 0, 3, and 1 for 1, 3, and 4, respectively. Supramolecular lone‐pair–π‐ring interactions are reported for the first time for the pyC{CN}NO– ligand and its importance in the crystal packing is discussed.
Synthesis of the Sesquiterpenes Albicanol, Drimanol, and Drimanic Acid, and the Marine Sesquiterpene Hydroquinone Deoxyspongiaquinol
Authors: Göhl Matthias , Seifert Karlheinz 
Published: September 2014

AbstractA TiIII‐mediated radical cyclization cascade has been used for the synthesis of the sesquiterpenes (+)‐albicanol, (+)‐drimanol, and (+)‐drimanic acid. Starting from all‐trans‐farnesol, (+)‐albicanol could be prepared in seven steps in an overall yield of 14.9 %. Furthermore, a highly diastereoselective hydrogenation of (+)‐albicanol to give (+)‐drimanol has been developed. We used the synthesized (+)‐drimanic acid to achieve the first synthesis of the marine sesquiterpene hydroquinone deoxyspongiaquinol and the quinone deoxyspongiaquinone. Thus, this synthetic strategy gave access to five natural products.
Characterization of Nano‐Titania Modified CdS /Polysulfide Electrolyte Interface by Utilizing MottSchottky and Electrochemical Impedance Spectroscopy
Authors: Pareek Alka , Paik Pradip , Borse Pramod H. 
Published: September 2014

AbstractPhotoelectrochemical (PEC) H2 generation is a green energy solution to upcoming energy crises. We have modified photo‐unstable CdS thin film with TiO2‐nanoparticles. Semiconductor electrolyte interface (SEI) of modified CdS surface using MottSchottky (MS) analysis is used to evaluate the relative band edge positions and flat‐band potential (VFB). Effect of applied AC‐frequency, electrolyte pH and electrode surface modification, on VFB and carrier‐concentration is studied. Modified photoanode shows high photocurrent and stability, than bare CdS photoanode. Improved performance of modified photoanode is attributed to the higher recombination lifetime of the charge carrier as deduced by electrochemical impedance spectroscopy.
Nonenzymatic Hydrogen Peroxide Electrochemical Sensor Based on Au‐HS/SO3H‐PMO (Et) Nanocomposite
Authors: Jia Feifei , Zhong Hui , Zhu Fengxia , Li Xiaorong , Wang Yinzhu , Cheng Zhipeng , Zhang Lili , Sheng Zhenhuan , Guo Liping 
Published: September 2014

AbstractA newly nonenzymatic sensor for hydrogen peroxide (H2O2) based on the (Au‐HS/SO3H‐PMO (Et)) nanocomposite is demonstrated. The electrochemical properties of the as‐prepared nanocomposite were studied. It displayed an excellent performance towards H2O2 sensing in the linear response range from 0.20 µM to 4.30 mM (R=0.9999) with a sensitivity of 6.35×102 µA µM−1 cm−2 and a low detection limit of 0.0499 µM. Furthermore, it was not affected by electroactive interference species. These features proved that the modified electrode was suitable for determination of H2O2.
Envisioning an Evaluation Curriculum to Develop Culturally Responsive Evaluators and Support Social Justice
Authors: Collins Prisca M. , Kirkhart Karen E. , Brown Tanya 
Published: September 2014

AbstractThis chapter describes the theoretical framework underlying the Graduate Education Diversity Internship (GEDI) program curriculum and discusses how the program evolved over time. It describes the various components of the program, plus factors that influenced curriculum content and format. The chapter also discusses four levels of intended program outcomes: individual, organizational, community, and professional. As former coordinators and instructor of the program, we explain how the theoretical framework we adopted guided the development of culturally responsive evaluators committed to social justice and social change. The chapter concludes by examining the impact of program participation on the instructors, suggesting pathways of influence that lie outside the original conceptualization of the program, including how the synergy of evolving theory and curriculum enriched the program.