bluuebunny/crossref_metadata_2025 huggingface dataset:
The issue of sustainable urban development in a neoliberal age. Discursive entanglements and disputes
Authors: Skrede Joar
Published: September 2014

The city of Oslo, the Norwegian capital, is in the midst of executing a huge urban waterfront project in Bjørvika. This project has triggered several years of public debate. A key concept in the development project is “sustainable development”, but it is unclear what the concept implies. Several interests are involved which emphasise different goals and different values. In this article, a discourse analysis of the concept, in this particular context, is conducted. Five discourses are identified, which overlap as well as collide. Special attention is paid to how the respective discourses are related to a neoliberal form of government, and as part of the analysis, a discussion of how cultural heritage is used to increase the city’s attractiveness is undertaken. This article concludes that planning for a sustainable use of cultural heritage should imply establishing a reflective cultural policy not subsumed under economic sustainability.
Striden om typografiens sjel – Max Bill versus Jan Tschichold
Authors: Rannem Øyvin
Published: September 2014

Den korte og følelsesladede debatten mellom den tyske typografen og designeren Jan Tschichold og den sveitsiske arkitekten og designeren Max Bill fra 1946 berører noen sentrale estetiske og funksjonelle aspekter ved typografi og grafisk design. Foranledningen for debatten var at Tschichold i løpet av krigsårene 1940–45 hadde vendt seg mot sine tidligere standpunkter og gått til angrep på funksjonalismen og «den nye typografien». Isteden tok han den tradisjonelle, symmetriske typografien i forsvar og gav den en fornyelse og en kvalitetsheving. Artikkelen tar for seg debatten og kommenterer de ulike standpunktene i lys av den senere faghistorien, og fokuserer spesielt på hvordan ideologi og tidsavhengig tanke­gods kan påvirke argumenter om funksjonalitet og estetikk.
Relating Systems Thinking & Design 2013. Emerging Contexts for Systemic Design
Authors: Sevaldson Birger
Published: September 2014

AHO – Oslo School of Architecture & Design, Norway, invites to the Relating Systems Thinking and Design to a free and open symposium over two days 9th-11th October 2013, with a preceding full day with diverse workshops and a subsequent special issue in FORMakademisk.
Explorative Materiality and Knowledge. The Role of Creative Exploration and Artefacts in Design Research
Authors: Niedderer Kristina
Published: September 2014

Juxtaposing the nature of design and the foundations of research in the traditional science and humanities disciplines puts their differences into sharp relief. The comparison highlights the key characteristics of design – its creative and experiential nature – which any design research must take into account, as well as the theoretical foundations of research. The aim of this article is to develop an understanding of the ontological, epistemological and methodological issues of design research, and to offer a framework that can embrace equally the notions of creativity and experiential knowledge, and of academic rigour. Furthermore,the potential roles of the design process and artefact within research are examined within this theoretical framework, which suggests that design processes and artefacts can – if appropriately framed – play an important partin the research process, facilitating an approach commensurate with the aims ofdesign enquiry. A case study of the Niedderer’s own work serves to illustratethe balance and integration of theory and (creative) practice within the research process, and how this integration can enable a multi-layered contribution to the theoretical and practical advancement of the field.
Urban routes and commuting bicyclist’s aesthetic experience
Authors: Stefansdottir Harpa
Published: September 2014

The present study examines whether and in what way aesthetic experience is involved in the judged quality of bicyclist’s route which they have chosen to ride between home and work. In this respect it is considered important to distinguish aesthetic experience from experience that is related to the influence of instrumental or functional features. The aesthetic impact is primarily related to features that stimulate emotional well-being when cycling. An online survey was conducted in three Nordic cities, Odense, Trondheim and Reykjavík, concentrating on cycling in different urban surroundings. The interpretation of the meanings and values associated with certain features or characteristics that influenced the commuting cyclists’ aesthetic experience is in this paper based on three theoretical viewpoints: (1) the phenomenology of perception and experience, (2) urban design theory and (3) environmental aesthetic theories and methods. The last theory involves the interpretation of experience from the environment into aesthetic meaning. The results of the survey indicate that aesthetic experience is of value to most of the respondents and is, therefore, of importance in developing the quality of bicycle routes for commuting. Greenery and contact with the natural environment and distance from motorised traffic are the most important influences on pleasurable aesthetic experience.
The winter helium bulge revisited
Authors: Liu Xianjing , Wang Wenbin , Thayer Jeffrey P. , Burns Alan , Sutton Eric , Solomon Stanley C. , Qian Liying , Lucas Greg
Published: September 2014

A newly implemented helium module in the National Center for Atmospheric Research‐Thermosphere Ionosphere Electrodynamics general circulation model offers the first opportunity in three decades to describe helium behavior in the context of a first principles, self‐consistent model and to test early theories of wintertime helium bulge formation. This study shows general agreement with the findings of Reber and Hays (1973) but articulates the definitive role of vertical advection in the bulge formation. Our findings indicate vertical advection and molecular diffusion are the dominate processes responsible for the solstice helium distribution. Horizontal winds indirectly contribute to the helium bulge formation by their divergent wind field that leads to vertical winds in order to maintain thermosphere mass continuity. As a minor gas, thermospheric helium does not contribute to mass continuity and its distribution is dictated by more local interactions and constraints.
Influence of the interplanetary driver type on the durations of the main and recovery phases of magnetic storms
Authors: Yermolaev Yu. I. , Lodkina I. G. , Nikolaeva N. S. , Yermolaev M. Yu.
Published: September 2014

We study the durations of the main and recovery phases of magnetic storms induced by different types of large‐scale solar‐wind streams (Sheath, magnetic cloud (MC), Ejecta, and corotating interaction region (CIR)) on the basis of OMNI data for 1976–2000. The durations of both the main and recovery phases depend on the type of interplanetary drivers. On average, the duration of the main phase of storms induced by compressed regions (CIR and Sheath) is shorter than for MC and Ejecta, while the duration of the recovery phase of CIR‐ and Sheath‐induced storms is longer. Analysis of the durations of individual storms shows that the durations of the main and recovery phases anticorrelate for CIR‐ and Sheath‐induced storms and there is no dependence between them for (MC + Ejecta)‐induced storms.
A novel data assimilation methodology for predicting lithology based on sequence labeling algorithms
Authors: Jeong Jina , Park Eungyu , Han Weon Shik , Kim Kue‐Young
Published: September 2014

A hidden Markov model (HMM) and a conditional random fields (CRFs) model for lithological predictions based on multiple geophysical well‐logging data are derived for dealing with directional nonstationarity through bidirectional training and conditioning. The developed models were benchmarked against their conventional counterparts, and hypothetical boreholes with the corresponding synthetic geophysical data including artificial errors were employed. In the three test scenarios devised, the average fitness and unfitness values of the developed CRFs model and HMM are 0.84 and 0.071 and 0.81 and 0.084, respectively, while those of the conventional CRFs model and HMM are 0.78 and 0.091 and 0.77 and 0.099, respectively. Comparisons of their predictabilities show that the models designed for directional nonstationarity clearly perform better than the conventional models for all tested examples. Among them, the developed linear‐chain CRFs model showed the best or close to the best performance with high predictability and a low training data requirement.
Formation and distribution of sea ice in the Gulf of St. Lawrence: A process‐oriented study using a coupled ocean‐ice model
Authors: Urrego‐Blanco Jorge , Sheng Jinyu
Published: September 2014

A coupled ocean‐ice model for the eastern Canadian shelf is used to examine main physical processes affecting sea ice conditions in the Gulf of St. Lawrence (GSL) and adjacent waters. The coupled model is based on NEMO and uses OPA9 as the ocean circulation component and LIM2 as the ice model. The coupled model is forced by atmospheric reanalysis fields produced by Large and Yeager (2004). The model results are used to examine the roles of thermodynamics and dynamics on sea ice distributions and patterns of ice production and melting, and the influence of ice capping on the circulation in the study region. Analysis of model results indicates that local production of sea ice is important in shallower areas over the northern and western GSL. Equatorward advection of sea ice from the St. Lawrence Estuary is affected significantly by the Gaspé Current. An index is used to quantify the relative importance of thermodynamic and dynamics of sea ice in the GSL. It is found that both thermodynamics and dynamics are important over most of the GSL, except for waters around Anticosti Island, in the southeastern Gulf, and over the eastern Scotian Shelf, where dynamics (or sea ice movements) are the most important mechanism for the presence of sea ice. The study also demonstrates that ice capping significantly reduces the strength of the winter circulation in the GSL.
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

The 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.
Further evidence for links between facial width‐to‐height ratio and fighting success: Commentary on Zilioli et al. (2014)
Authors: Třebický Vít , Fialová Jitka , Kleisner Karel , Roberts S. Craig , Little Anthony C. , Havlíček Jan
Published: September 2014

Recent research has reported an association between facial width‐to‐height ratio (fWHR) and both fighting performance and judgments of formidability in a sample of mixed martial arts (MMA) combatants. The results provide evidence of fWHR being associated with sporting performance and aggression in men. However, it has been argued that the effect of fWHR might be a by‐product of associations between body size and behavioral measures. Here we tested whether fWHR is associated with perceived aggressiveness, fighting ability and success in physical confrontation, while controlling for body size, also in a sample of MMA fighters. We found that perceived fighting ability was predicted by weight but not by fWHR. In contrast, both fWHR and body weight independently predicted perceived aggressiveness. Furthermore, we found positive associations between fWHR and fighting performance which appear to be independent of body size. Our findings provide further support for the proposal that fWHR is associated with fighting ability and perceived aggression, and that these effects are independent of body size. Therefore, fWHR might be considered as a viable and reliable marker for inference of success in male intra‐sexual competition. Aggr. Behav. 41:331–334, 2015. © 2014 Wiley Periodicals, Inc.
Eliciting Information and Detecting Lies in Intelligence Interviewing: An Overview Of Recent Research
Authors: Vrij Aldert , Granhag Pär Anders
Published: September 2014

Traditional 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

Objective

The 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.

Methods

SSc 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.

Results

A 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%.

Conclusion

The 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

Quantum 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

Ursolic 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

Microbial 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

Epimerization 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

A 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

Although 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

Metal@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

A 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

To 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

The 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

Three 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

A 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

Photoelectrochemical (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

A 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

This 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.
Mentorship and the Professional Development of Culturally Responsive Evaluators in the American Evaluation Association's Graduate Education Diversity Internship (GEDI) Program
Authors: Gómez Ricardo L. , Ali Asma , Casillas Wanda
Published: September 2014

In this study, we used Q methodology to investigate perspectives on mentorship among alumni of the Graduate Education Diversity Internship (GEDI) program. We asked participants to think retrospectively and give their opinion on the most important characteristics a GEDI mentor should have, based on what they would have liked or needed when they participated in the GEDI program. Three different perspectives on mentoring emerged from participants. They show that mentoring is not unidimensional; that perceptions and expectations of mentoring are defined to a great extent by the professional needs, background, and expectation of the participants. We suggest that the program takes those needs and expectations into consideration and use them as criteria for selecting mentors.
Socializing Emerging Evaluators: The Use of Mentoring to Develop Evaluation Competence
Authors: Bertrand Jones Tamara
Published: September 2014

The interdisciplinary nature of evaluation necessitates that emerging evaluators, those within the first five years in the evaluation profession, operate competently within the profession, and receive an extensive and deliberate socialization to the field. Mentoring is a key component to integrating these new evaluators into the field and one way that socialization takes place. In this chapter, survey data from GEDI participants are used to describe how the Graduate Education Diversity Internship (GEDI) program influences the socialization of diverse emerging scholars, specifically using mentoring relationships to facilitate the development of evaluation competence. Survey data exploring the interns’ formal and informal mentoring relationships suggest that informal mentoring relationships were more effective and yield more support for psychosocial development and exposure to evaluation‐related knowledge and competence in comparison with formal mentoring relationships.
Topology optimisation for natural convection problems
Authors: Alexandersen Joe , Aage Niels , Andreasen Casper Schousboe , Sigmund Ole
Published: September 2014

This paper demonstrates the application of the density‐based topology optimisation approach for the design of heat sinks and micropumps based on natural convection effects. The problems are modelled under the assumptions of steady‐state laminar flow using the incompressible Navier–Stokes equations coupled to the convection‐diffusion equation through the Boussinesq approximation. In order to facilitate topology optimisation, the Brinkman approach is taken to penalise velocities inside the solid domain and the effective thermal conductivity is interpolated in order to accommodate differences in thermal conductivity of the solid and fluid phases. The governing equations are discretised using stabilised finite elements and topology optimisation is performed for two different problems using discrete adjoint sensitivity analysis. The study shows that topology optimisation is a viable approach for designing heat sink geometries cooled by natural convection and micropumps powered by natural convection. Copyright © 2014 John Wiley & Sons, Ltd.
Flooding in urban drainage systems: coupling hyperbolic conservation laws for sewer systems and surface flow
Authors: Borsche R. , Klar A.
Published: September 2014

In this paper, we propose a model for a sewer network coupled to surface flow and investigate it numerically. In particular, we present a new model for the manholes in storm sewer systems. It is derived using the balance of the total energy in the complete network. The resulting system of equations contains, aside from hyperbolic conservation laws for the sewer network and algebraic relations for the coupling conditions, a system of ODEs governing the flow in the manholes. The manholes provide natural points for the interaction of the sewer system and the runoff on the urban surface modeled by shallow‐water equations. Finally, a numerical method for the coupled system is presented. In several numerical tests, we study the influence of the manhole model on the sewer system and the coupling with 2D surface flow. Copyright © 2014 John Wiley & Sons, Ltd.
Prognosis of untreated hepatocellular carcinoma
Authors: Giannini Edoardo G. , Farinati Fabio , Ciccarese Francesca , Pecorelli Anna , Rapaccini Gian Lodovico , Di Marco Mariella , Benvegnù Luisa , Caturelli Eugenio , Zoli Marco , Borzio Franco , Chiaramonte Maria , Trevisani Franco ,   for the Italian Liver Cancer (ITA.LI.CA) group
Published: September 2014

The prognosis of untreated patients with hepatocellular carcinoma (HCC) is heterogeneous, and survival data were mainly obtained from control arms of randomized studies. Clinical practice data on this topic are urgently needed, so as to help plan studies and counsel patients. We assessed the prognosis of 600 untreated patients with HCC managed by the Italian Liver Cancer Group. Prognosis was evaluated by subdividing patients according to the Barcelona Clinic Liver Cancer (BCLC) classification. We also assessed the main demographic, clinical, and oncological determinants of survival in the subgroup of patients with advanced HCC (BCLC C). Advanced (BCLC C: n = 138; 23.0%) and end‐stage HCC (BCLC D; n = 210; 35.0%) represented the majority of patients. Overall median survival was 9 months, and the principal cause of death was tumor progression (n = 279; 46.5%). Patients' median survival progressively and significantly decreased as BCLC stage worsened (BCLC 0: 38 months; BCLC A: 25 months; BCLC B: 10 months; BCLC C: 7 months; BCLC D: 6 months; P < 0.0001). Female gender (hazard ratio [HR] = 0.55; 95% confidence interval [CI] = 0.33‐0.90; P = 0.018), ascites (HR = 1.81; 95% CI = 1.21‐2.71; P = 0.004), and multinodular (>3) HCC (HR = 1.79; 95% CI = 1.21‐2.63; P = 0.003) were independent predictors of survival in patients with advanced HCC (BCLC C). Conclusion: BCLC adequately predicts the prognosis of untreated HCC patients. In untreated patients with advanced HCC, female gender, clinical decompensation of cirrhosis, and multinodular tumor are independent prognostic predictors and should be taken into account for patient stratification in future therapeutic studies. (Hepatology 2015;61:184–190)
Liver is the major source of elevated serum lipocalin‐2 levels after bacterial infection or partial hepatectomy: A critical role for IL‐6/STAT3
Authors: Xu Ming‐Jiang , Feng Dechun , Wu Hailong , Wang Hua , Chan Yvonne , Kolls Jay , Borregaard Niels , Porse Bo , Berger Thorsten , Mak Tak W. , Cowland Jack B. , Kong Xiaoni , Gao Bin
Published: September 2014

Lipocalin‐2 (LCN2) was originally isolated from human neutrophils and termed neutrophil gelatinase‐associated lipocalin (NGAL). However, the functions of LCN2 and the cell types that are primarily responsible for LCN2 production remain unclear. To address these issues, hepatocyte‐specific Lcn2 knockout (Lcn2
Hep–/–) mice were generated and subjected to bacterial infection (with Klesbsiella pneumoniae or Escherichia coli) or partial hepatectomy (PHx). Studies of Lcn2
Hep–/– mice revealed that hepatocytes contributed to 25% of the low basal serum level of LCN2 protein (∼62 ng/mL) but were responsible for more than 90% of the highly elevated serum LCN2 protein level (∼6,000 ng/mL) postinfection and more than 60% post‐PHx (∼700 ng/mL). Interestingly, both Lcn2
Hep–/– and global Lcn2 knockout (Lcn2
–/–) mice demonstrated comparable increases in susceptibility to infection with K. pneumoniae or E. coli. These mice also had increased enteric bacterial translocation from the gut to the mesenteric lymph nodes and exhibited reduced liver regeneration after PHx. Treatment with interleukin (IL)‐6 stimulated hepatocytes to produce LCN2 in vitro and in vivo. Hepatocyte‐specific ablation of the IL‐6 receptor or Stat3, a major downstream effector of IL‐6, markedly abrogated LCN2 elevation in vivo. Furthermore, chromatin immunoprecipitation (ChIP) assay revealed that STAT3 was recruited to the promoter region of the Lcn2 gene upon STAT3 activation by IL‐6. Conclusion: Hepatocytes are the major cell type responsible for LCN2 production after bacterial infection or PHx, and this response is dependent on IL‐6 activation of the STAT3 signaling pathway. Thus, hepatocyte‐derived LCN2 plays an important role in inhibiting bacterial infection and promoting liver regeneration. (Hepatology 2015;61:692‐702)
Bringing out the Potential of Wild‐type Cytochrome P450s using Decoy Molecules: Oxygenation of Nonnative Substrates by Bacterial Cytochrome P450s
Authors: Shoji Osami , Watanabe Yoshihito
Published: September 2014

To bring out the potential of wild‐type cytochrome P450s, we have developed a series of “decoy molecules” to change their high substrate specificity without any mutagenesis. Decoy molecules are inert dummy substrates with structures that are very similar to those of natural substrates. The decoy molecules force long‐alkyl‐chain fatty acid hydroxylases (P450BSβ, P450SPα, and P450BM3) to generate the active species and to catalyze oxidation of various substrates other than fatty acids. Interestingly, the catalytic activity was highly dependent on the structure of decoy molecules. Furthermore, the enantioselectivity of reactions catalyzed by P450BSβ and P450SPα was also dependent on the structure of decoy molecules. The decoy molecule system allows us to control reactions catalyzed by wild‐type enzymes by designing decoy molecules.
Protein Needles as Molecular Templates for Artificial Metalloenzymes
Authors: Inaba Hiroshi , Kitagawa Susumu , Ueno Takafumi
Published: September 2014

Construction of artificial metalloenzymes based on protein assemblies is a promising strategy for the development of new catalysts, because the three‐dimensional nanostructures of proteins with defined individual sizes can be used as molecular platforms that allow the arrangement of catalytic active centers on their surfaces. Protein needles/tubes/fibers are suitable for supporting various functional molecules, including metal complexes, synthetic molecules, metal nanoparticles, and enzymes with high densities and precise locations. Compared with bulk systems, the protein tube‐ and fiber‐based materials have higher activities for catalytic reactions and electron transfer, as well as enhanced functions when used in electronic devices. The natural and synthetic protein tubes and fibers are constructed by self‐assembly of monomer proteins or peptides. For more precise designs of arrangements of metal complexes, we have developed a new conceptual framework, based on the isolation of a robust needle structure from the cell‐puncturing domains of a bacteriophage. The artificial protein needle shows great promise for use in creating efficient catalytic systems by providing the means to arrange the locations of various metal complexes on the protein surface. In this account, we discuss the recent development of protein needle‐based metalloenzymes, and the future developments we are anticipating in this field.
Concerns regarding nanosized titanium dioxide nasal exposure and neurotoxicity study by Ze et al.
Authors: Bencsik Anna , Lestaevel Philippe
Published: September 2014

Scientific articles dealing with nanotoxicology are particularly awaited and important, as in the field of nanotechnology, a relatively new domain; they likely have a significant impact not only on our perception of the risk and danger potentially associated with nanomaterials but also on regulatory decisions with regard to their use in consumer products. Because nanotoxicology refers to the work of researchers from different domains of expertise, it appears also more difficult to secure accurate review and thus accurate conclusions. In that context, particular attention must be drawn on these studies. Still for the readers of such articles, of which most of are not experts in several aspects of nanotoxicology it would be tempting to take the messages for granted, thinking the studies are well conducted and reported with accuracy. In the case of the article by Ze and colleagues, we have noticed a certain number of critical comments that should be brought to the attention of the readers of J. Biomed Mater res A, because this study presents several problems. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 2198–2200, 2015.