bluuebunny/crossref_metadata_2025 huggingface dataset:
Recording and Interpreting Work‐Related Daydreams: Effects on Vocational Self‐Concept Crystallization
Authors: Pisarik Christopher T. , Currie Lacy K.
Published: September 2015

This mixed‐methods study examined the effects of recording and interpreting work‐related daydreams on vocational self‐concept crystallization and attitudes toward daydreams. Fifty‐one college students were assigned to 1 of 2 experimental groups—daydream journal group (n = 15) and daydream interpretation group (n = 18)—and a control group (n = 18). Data were analyzed using analyses of covariance. At posttest, both experimental groups showed higher levels of vocational self‐concept crystallization than the control group, and the daydream interpretation group perceived their daydreams as more relevant than the control group. Qualitative data were collected via written postintervention surveys and embedded as a supplement to the quantitative design. The qualitative data support the findings that participants in the experimental groups gained a greater awareness and clarity regarding their vocational self‐concepts and a greater belief in the relevancy of work‐related daydreams.
Self‐Help Career Services: A Case Report
Authors: Kronholz Julia F.
Published: September 2015

Self‐help career services represent an important form of career intervention rarely described in the literature. Using a case‐report approach, the author describes this type of career intervention, which was guided by cognitive information processing theory and Holland's () typological theory. The report offers an example of appropriately identifying client readiness to engage in career counseling using a 3‐tier model for service delivery composed of direct, brief, and self‐help interventions. It also demonstrates an effective method for translating theory to practice, a particularly critical need in the career development field. The outcome of the intervention supports a differentiated model of career services that increases client accessibility to those services.
Making Our Way Through: Voices of Hispanic Counselor Educators
Authors: Lerma Eunice , Zamarripa Manuel X. , Oliver Marvarine , Cavazos Vela Javier
Published: September 2015

Through 23 open‐ended questionnaires and 8 individual interviews, this phenomenological study explored the experiences of Hispanic men and women (N = 23) who completed doctoral degrees in counselor education. Six themes were identified: family role models, educational support, parental expectations, ethnic identity, acculturation/cultural expectations, and intrinsic motivation.
From School Counselor to Counselor Educator: A Phenomenological Study
Authors: Milsom Amy , Moran Kristen
Published: September 2015

Through a phenomenological study, the experiences of 8 early‐career school counselor educators who entered academia directly from positions as P–12 school counselors were examined. Results revealed that the participants experienced numerous challenges and supports related to their transition. Recommendations for counselor educators, doctoral students, and new faculty are provided.
Chlorination‐Promoted Skeletal‐Cage Transformations of C88 Fullerene by C2 Losses and a CC Bond Rotation
Authors: Yang Shangfeng , Wei Tao , Scheurell Kerstin , Kemnitz Erhard , Troyanov Sergey I.
Published: September 2015

High‐temperature chlorination of fullerene C88 (isomer 33) with VCl4 gives rise to skeletal transformations affording several nonclassical (NC) fullerene chlorides, C86(NC1)Cl24/26 and C84(NC2)Cl26, with one and two heptagons, respectively, in the carbon cages. The branched skeletal transformation including C2 losses as well as a Stone–Wales rearrangement has been comprehensively characterized by the structure determination of two intermediates and three final chlorination products. Quantum‐chemical calculations demonstrate that the average energy of the CCl bond is significantly increased in chlorides of nonclassical fullerenes with a large number of chlorinated sites of pentagon–pentagon adjacency.
One‐Pot Synthesis of Zeolitic Strong Solid Bases: A Family of Alkaline‐Earth Metal‐Containing Silicalite‐1
Authors: Zhou Yu , Jin Yanhua , Wang Meng , Zhang Wei , Xie Jingyan , Gu Jing , Wen Haimeng , Wang Jun , Peng Luming
Published: September 2015

Fabricating stable strong basic sites in well‐preserved crystallized zeolitic frameworks still remains a difficult issue. Here, we reported a family of MFI‐type metallosilicate zeolites, AeS‐1 (Ae: alkaline‐earth metal ions of Mg, Ca, Sr or Ba; S‐1: silicalite‐1) through a direct one‐pot hydrothermal method involving the acidic co‐hydrolysis/condensation of the silica precursor with the Ae salts. Step‐by‐step full characterizations were designed and conducted for in‐depth discussion of the Ae status in AeS‐1. Strong basicity (H_≈22.5–26.5) was detected in AeS‐1. The basicity was further confirmed by CO2 sorption measurements, 13C NMR spectra of chloroform‐adsorbed samples, and 1H→13C and 1H→29Si cross‐polarization magic‐angle spinning NMR spectra of ethyl cyanoacetate‐adsorbed samples. The results of Knoevenagel condensations demonstrated the excellent solid base catalysis of AeS‐1, which showed high activity, reusability, and shape‐selectivity, all of which are explained by Ae‐derived zeolitic intracrystalline strong basic sites.
Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation, Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)
Authors: Braunschweig Holger , Damme Alexander , Dück Klaus , Fuß Marco , Hörl Christian , Kramer Thomas , Krummenacher Ivo , Kupfer Thomas , Paprocki Valerie , Schneider Christoph
Published: September 2015

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η5‐C5H4Li)(η6‐C6H5Li)]⋅pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] and [Mn(η5‐C5H4)(η6‐C6H5)SiPh2], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η5‐C5H4)(η6‐C6H5)Sn2tBu4] with elemental sulfur was shown to proceed through the expected oxidative addition of the SnSn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] with [Pt(PEt3)3] showed that an unexpected, unselective insertion into the CipsoSn bonds of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] had occurred.
Synergetic Effect of Dual Co‐catalysts on the Activity of p‐Type Cu2O Crystals with Anisotropic Facets
Authors: Li Rengui , Tao Xiaoping , Chen Ruotian , Fan Fengtao , Li Can
Published: September 2015

Spatial separation of reduction sites and oxidation sites to inhibit the recombination of photogenerated electrons and holes plays a vital role in improving the efficiency of photocatalyst systems. It is very challenging to rationally deposit cocatalysts on the right facets (sites), namely, the reduction cocatalyst on the reduction facets (sites) and the oxidation cocatalyst on the oxidation facets (sites). Herein, we report that the reduction and oxidation cocatalysts can be selectively constructed on the different facets of p‐type Cu2O crystals with anisotropic facets, but not on the Cu2O crystal with isotropic facets. The deposition of dual cocatalysts on the different facets resulted in a remarkable synergetic effect in the photocatalytic performance, which could be attributed to the spatial separation of the photogenerated charges between facets. Our work reports an instructive strategy for constructing high‐efficiency photocatalyst systems for solar energy conversion.
Photoinduced Aminocarbonylation of Aryl Iodides
Authors: Kawamoto Takuji , Sato Aoi , Ryu Ilhyong
Published: September 2015

Transition metal‐catalyzed aminocarbonylation of aryl halides with CO and amines, pioneered by Heck and co‐workers in the 1970s, is among the most commonly employed reactions to make aromatic amides. A catalyst‐free aminocarbonylation of aryl iodides with CO and amines, which simply uses photoirradiation conditions by Xe‐lamp, has now been developed. This methodology shows broad functional‐group tolerance, including that of heteroaromatic amides. A hybrid radical/ionic chain mechanism, involving electron transfer from zwitterionic radical intermediates generated by nucleophilic attack of amines to aroyl radicals, is proposed.
Interest alignment for joint business development: How global software houses and consulting firms work together in the enterprise systems sector
Authors: Neves da Rocha Fábio , Bataglia Walter
Published: September 2015

Despite the relatively long history of strategic alliances in the enterprise systems sector, studies examining the relationships between software houses and consulting firms have been rare and fragmented, particularly those related to the mechanisms that promote interest alignment for delivering a joint value proposition to the market. Through the cross‐analysis of two case studies, we identify 10 mechanisms that are regularly used for interest alignment purposes as well as counterpoints that contribute to the literature regarding the search for a consistent explanation for the longevity of hybrid organizational forms. Additionally, the study provides some insights related to the impact of innovation massification on competitiveness, partners' interdependence, and the presence of complementary contracts along with insights into the coexistence and interaction of other mechanisms that may help to explain the persistent existence of hybrid organizational forms in markets. Copyright © 2015 ASAC. Published by John Wiley & Sons, Ltd.
Attapulgite as Potential Adsorbent for Dissolved Organic Carbon From Oily Water
Authors: Al. Haddabi Mansour , Vuthaluru Hari , Znad Hussein , Ahmed Mushtaque
Published: September 2015

The adsorption capacity of attapulgite, a natural clay, for the removal of dissolved organic carbon (DOC) from oily water was investigated in a batch system. The aim of this study was to understand the mechanism associated with the removal of DOC by attapulgite. The effectiveness of attapulgite to adsorb DOC was investigated as a function of equilibrium time, initial DOC concentration, solution pH, temperature, and attapulgite concentration. Two particle sizes of attapulgite were used, granular (1 mm) and powder (0.25 mm). In most cases, the equilibrium data fit best with the Langmuir isotherm. The maximum monolayer coverage was found to be 31 mg/g for granular and 65 mg/g for powder attapulgite. The separation factor, RL, from the Langmuir isotherm and, n, the constant from the Freundlich isotherm indicated favorable adsorption. Changes in the pH of the oily water had no significant influence on the adsorption capacity. The adsorption follows the pseudo‐second order model. The governing transport mechanisms in the sorption process appear to be both external mass transfer and intra‐particle diffusion. The adsorption process was found exothermic in nature. The Langmuir isotherm model equation was adopted to design a single‐stage batch absorber for DOC adsorption onto attapulgite. The study demonstrated that attapulgite can be utilized as a potential alternative low‐cost adsorbent for the removal of DOC from oily water.
Phage Selection of Bicyclic Peptide Ligands of the Notch1 Receptor
Authors: Urech‐Varenne Charlotte , Radtke Freddy , Heinis Christian
Published: September 2015

Precise regulation of the Notch signaling pathway is crucial, as increases or deficiencies in signaling are associated with diseases, including a wide range of cancers. Recent studies have demonstrated that monoclonal antibodies that bind and stabilize the structure of the negative regulatory region (NRR) in the extracellular domain of the Notch receptor can inhibit Notch signaling. In this work, we posed the question whether bicyclic peptides, being around 100‐fold smaller than antibodies, can also stabilize the NRR and inhibit Notch signaling. Bicyclic peptides that bind the NRR of human Notch1 were isolated from combinatorial libraries by phage display. Affinity maturation yielded ligands with dissociation constant (Kd) values as low as 150 nM. The bicyclic peptides increased the melting temperature of the NRR by up to 8 °C, thus substantially stabilizing the protein structure, but they did not inhibit Notch signaling in cellular assays. Although Notch signaling could not be inhibited, this work demonstrates that phage‐selected bicyclic peptides can stabilize proteins; this capacity of bicyclic peptides may be exploited for modulating the conformation of other disease targets.
Phototoxic Activity and DNA Interactions of Water‐Soluble Porphyrins and Their Rhenium(I) Conjugates
Authors: Mion Giuliana , Gianferrara Teresa , Bergamo Alberta , Gasser Gilles , Pierroz Vanessa , Rubbiani Riccardo , Vilar Ramon , Leczkowska Anna , Alessio Enzo
Published: September 2015

In the search for alternative photosensitizers for use in photodynamic therapy (PDT), herein we describe two new water‐soluble porphyrins, a neutral fourfold‐symmetric compound and a +3‐charged tris‐methylpyridinium derivative, in which either four or one [1,4,7]‐triazacyclononane (TACN) units are connected to the porphyrin macrocycle through a hydrophilic linker; we also report their corresponding tetracationic ReI conjugates. The in vitro (photo)toxic effects of the compounds toward the human cell lines HeLa (cervical cancer), H460M2 (non‐small‐cell lung carcinoma), and HBL‐100 (non‐tumorigenic epithelial cells) are reported. Three of the compounds are not cytotoxic in the dark up to 100 μm, and the fourfold‐symmetric couple revealed very good phototoxic indexes (PIs). The intracellular localization of all derivatives was studied in HeLa cells by confocal fluorescence microscopy. Although low nuclear localization was observed for some of them, it still prompted us to investigate their capacity to bind both quadruplex and duplex DNA; we observed significant selectivity in the tris‐methylpyridinium derivatives for G‐quadruplex interactions.
Differences in driver genes between smoking‐related and non–smoking‐related lung cancer in the Chinese population
Authors: Gou Lan‐Ying , Niu Fei‐Yu , Wu Yi‐Long , Zhong Wen‐Zhao
Published: September 2015

Recently, non–smoking‐related lung cancer was classified as an independent disease entity because it is different from tobacco‐associated lung cancer. Non–smoking‐related lung cancer occurs more often in women than men, and the predominant histological type is adenocarcinoma (ADC) rather than squamous cell carcinoma. Most of the driver gene alterations that have been identified in ADC in never‐smokers include epidermal growth factor receptor mutations, KRAS mutations, echinoderm microtubule–associated protein like 4/anaplastic lymphoma kinase fusion, and ROS1 fusion, among others. Meanwhile, significant progress has been made in the treatment of ADC. However, in comparison with ADC, no such available molecular targets exist for smoking‐associated lung cancer, for which treatment strategies are limited. Next‐generation sequencing has been widely applied to the discovery of more genetic profiles of lung cancers. This review summarizes the differences between smoking‐related and non–smoking‐related lung cancer as follows: different somatic mutation burdens, C:G→A:T transversions, common and novel driver genes, and treatment strategies. Overall, smoking‐related lung cancer is more complicated than non–smoking‐related lung cancer. Furthermore, we review the prevalence of driver genes in smoking‐associated and non–smoking‐associated lung cancers in the Chinese population. Cancer 2015;121:3069‐79. © 2015 American Cancer Society.
Emerging tobacco‐related cancer risks in China: A nationwide, prospective study of 0.5 million adults
Authors: Chen Zheng‐Ming , Peto Richard , Iona Andri , Guo Yu , Chen Yi‐Ping , Bian Zheng , Yang Ling , Zhang Wei‐Yuan , Lu Feng , Chen Jun‐Shi , Collins Rory , Li Li‐Ming ,   for the China Kadoorie Biobank Collaborative Group
Published: September 2015

BACKGROUND

In China, cigarette consumption has increased substantially since the 1980s, almost exclusively in men. This study was aimed at assessing the emerging cancer risks.

METHODS

A nationwide, prospective study recruited 210,259 men and 302,632 women aged 30 to 79 years from 10 areas of China from 2004 to 2008; approximately 18,000 incident cancers were recorded during 7 years of follow‐up. Cox regression yielded adjusted risk ratios (RRs) comparing smokers (including those who had stopped because of illness but not those who had stopped by choice) with never‐smokers.

RESULTS

Among men, 68% were smokers; their overall cancer risk was significantly increased (RR, 1.44; 95% confidence interval [CI], 1.37‐1.53), and it was greater in urban (RR, 1.55; 95% CI, 1.41‐1.70) than in rural areas (RR, 1.39; 95% CI, 1.30‐1.49). This excess accounted for 23% of all cancers between the ages of 40 and 79 years, with significantly elevated risks of lung cancer (RR, 2.51; 95% CI, 2.18‐2.90), liver cancer (RR, 1.32; 95% CI, 1.12‐1.54), stomach cancer (RR, 1.34; 95% CI, 1.16‐1.55), esophageal cancer (RR, 1.47; 95% CI, 1.24‐1.73), and an aggregate of 5 other minor sites (RR, 1.52; 95% CI, 1.25‐1.86). For lung cancer, the RRs were much greater for nonadenocarcinoma (RR, 5.83; 95% CI, 5.02‐6.77) than for adenocarcinoma (RR, 1.78; 95% CI, 1.36‐2.34). Among exsmokers (6.7%) who had stopped by choice, there was little excess cancer risk approximately 15 years after quitting. Among the few female smokers (3%), the overall cancer risk was also significantly increased (RR, 1.42; 95% CI, 1.28‐1.57). Smoking was estimated to cause approximately 435,000 new cancers per year in China (approximately 360,000 in men and approximately 75,000 in women).

CONCLUSIONS

In China, smoking now causes a quarter of all adult male cancers. High male uptake rates before the age of 20 years and nearly universal use of cigarettes foreshadow substantial tobacco‐attributed risks in China unless there is widespread cessation. Cancer 2015;121:3097‐106. © 2015 The Authors. Cancer published by Wiley Periodicals, Inc. on behalf of American Cancer Society.
Chinese consensus on early diagnosis of primary lung cancer (2014 version)
Authors: Hu Jie , Qian Gui-Sheng , Bai Chun-Xue ,   for the Lung Cancer Study Group of the Chinese Thoracic Society and the Chinese Alliance Against Lung Cancer Expert Group
Published: September 2015

The incidence and mortality of lung cancer in China have rapidly increased. Lung cancer is the leading cause of cancer death in China, possibly because of the inadequate early diagnosis of lung cancer. Reaching a consensus on early diagnostic strategies for lung cancer in China is an unmet needed. Recently, much progress has been made in lung cancer diagnosis, such as screening in high‐risk populations, the application of novel imaging technologies, and the use of minimally invasive techniques for diagnosis. However, systemic reviews of disease history, risk assessment, and patients' willingness to undergo invasive diagnostic procedures also need to be considered. A diagnostic strategy for lung cancer should be proposed and developed by a multidisciplinary group. A comprehensive evaluation of patient factors and clinical findings should be completed before treatment. Cancer 2015;121:3157‐64. © 2015 American Cancer Society.
Increased lung cancer mortality rates in the Chinese population from 1973‐1975 to 2004‐2005: An adverse health effect from exposure to smoking
Authors: Zhi Xiu-Yi , Zou Xiao‐Nong , Hu Mu , Jiang Yuan , Jia Man‐Man , Yang Gong‐Huan
Published: September 2015

BACKGROUND

Lung cancer incidence and mortality rates have increased substantially in China despite improvements in clinical diagnosis and treatment approaches as well as significant advances in the implementation of tobacco‐control policies in recent decades.

METHODS

Age‐standardized mortality rates and age‐specific rates of lung cancer in China were estimated for the periods 1973 to 1975, 1990 to 1992, and 2004 to 2005 using data from 3 National Death Surveys. Among patients with lung cancer who were identified from a hospital‐based information system, the percentages of ever‐smokers were analyzed according to histologic and demographic variables.

RESULTS

Age‐standardized mortality from lung cancer in China dramatically increased from 7.30 per 100,000 during 1973 through 1975 to 27.62 per 100,000 during 2004 through 2005. Increases in lung cancer age‐standardized mortality were consistent among men and women in urban and rural populations. Among men ages 75 to 79 years, lung cancer mortality increased remarkably to 453.67 per 100,000 in 2004 and 2005 (from 246.78 per 100,000 during 1990‐1992 and from 53.65 per 100,000 during 1973‐1975). Among 6674 patients with lung cancer who were identified from 2003 to 2007 from a hospital‐based database, 82.97% of men were ever‐smokers (73.35% of men with adenocarcinoma and 91.8% of men with squamous cell carcinoma), and 11.18% of women were ever‐smokers (6% of women with adenosquamous carcinoma and 39.02% of women with squamous cell carcinoma). Differences in the numbers of ever‐smokers were observed between age groups but not according to the year of diagnosis.

CONCLUSIONS

The consistent and rapid increases in lung cancer mortality rates observed in the Chinese population and the high prevalence of exposure to smoking in China prompt a strong call for the implementation of a comprehensive tobacco‐control policy and specific public health educational strategies. Cancer 2015;121:3107‐12. © 2015 American Cancer Society.
A MapReduce‐based parallel K‐means clustering for large‐scale CIM data verification
Authors: Deng Chuang , Liu Yang , Xu Lixiong , Yang Jie , Liu Junyong , Li Siguang , Li Maozhen
Published: September 2015

The Common Information Model (CIM) has been heavily used in electric power grids for data exchange among a number of auxiliary systems such as communication systems, monitoring systems, and marketing systems. With a rapid deployment of digitalized devices in electric power networks, the volume of data continuously grows, which makes verification of CIM data a challenging issue. This paper presents a parallel K‐means clustering algorithm for large‐scale CIM data verification. The parallel K‐means builds on the MapReduce computing model which has been widely taken up by the community in dealing with data‐intensive applications. A genetic algorithm‐based load‐balancing scheme is designed to balance the workloads among the heterogeneous computing nodes for a further improvement in computation efficiency. The performance of the parallel K‐means is initially evaluated in a small‐scale in‐house MapReduce cluster and subsequently evaluated in a commercial cloud computing platform. Finally, the parallel K‐means is evaluated in large‐scale simulated MapReduce environments. Both the experimental and simulation results show that the parallel K‐means reduces the CIM data‐verification time significantly compared with the sequential K‐means clustering, while generating a high level of precision in data verification. Copyright © 2015 John Wiley & Sons, Ltd.
Selection and replacement algorithms for memory performance improvement in Spark
Authors: Duan Mingxing , Li Kenli , Tang Zhuo , Xiao Guoqing , Li Keqin
Published: September 2015

As a parallel computation framework, Spark can cache repeatedly resilient distribution datasets (RDDs) partitions in different nodes to speed up the process of computation. However, Spark does not have a good mechanism to select reasonable RDDs to cache their partitions in limited memory. In this paper, we propose a novel selection algorithm, by which Spark can automatically select the RDDs to cache their partitions in memory according to the number of use for RDDs. Our selection algorithm speeds up iterative computations. Nevertheless, when many new RDDs are chosen to cache their partitions in memory while limited memory has been full of them, the system will adopt the least recently used (LRU) replacement algorithm. However, the LRU algorithm only considers whether the RDDs partitions are recently used while ignoring other factors such as the computation cost and so on. We also put forward a novel replacement algorithm called weight replacement (WR) algorithm, which takes comprehensive consideration of the partitions computation cost, the number of use for partitions, and the sizes of the partitions. Experiment results show that with our selection algorithm, Spark calculates faster than without the algorithm, and we find that Spark with WR algorithm shows better performance. Copyright © 2015 John Wiley & Sons, Ltd.
Similar Structural Dynamics for the Degradation of CH3NH3PbI3 in Air and in Vacuum
Authors: Alberti Alessandra , Deretzis Ioannis , Pellegrino Giovanna , Bongiorno Corrado , Smecca Emanuele , Mannino Giovanni , Giannazzo Filippo , Condorelli Guglielmo Guido , Sakai Nobuya , Miyasaka Tsutomu , Spinella Corrado , La Magna Antonino
Published: September 2015

We investigate the degradation path of MAPbI3 (MA=methylammonium) films over flat TiO2 substrates at room temperature by means of X‐ray diffraction, spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI2. We describe how this degradation product is structurally coupled with the original MAPbI3 lattice through the orientation of its constituent PbI6 octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH3NH2 or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.
Photoinduced Charge Separation in a Donor–Spacer–Acceptor Dyad with N‐Annulated Perylene Donor and Methylviologen Acceptor
Authors: Santoni Marie‐Pierre , Santoro Antonio , Salerno Tania M. G. , Puntoriero Fausto , Nastasi Francesco , Di Pietro M. Letizia , Galletta Maurilio , Campagna Sebastiano
Published: September 2015

The first donor–acceptor species in which a strongly emissive N‐annulated perylene dye is connected to a methylviologen electron acceptor unit via its macrocyclic nitrogen atom, is prepared by a stepwise, modular procedure. The absorption spectra, redox behavior, spectroelectrochemistry and photophysical properties of this dyad and of its model species are investigated, also by pump–probe fs transient absorption spectroscopy. Photoinduced oxidative electron transfer from the excited state of the dyad, centered on the N‐annulated perylene subunit, to the appended methyviologen electron acceptor takes place in a few ps. The charge‐separated species recombines in 19 ps. Our results indicate that N‐annulated perylene can be connected to functional units by taking advantage of the macrocyclic nitrogen, an option never used until now, without losing their properties, so opening the way to new designing approaches.
The Quest for Polysulfides in Lithium–Sulfur Battery Electrolytes: An Operando Confocal Raman Spectroscopy Study
Authors: Hannauer Julien , Scheers Johan , Fullenwarth Julien , Fraisse Bernard , Stievano Lorenzo , Johansson Patrik
Published: September 2015

The front cover artwork is provided by the groups of Prof. Lorenzo Stievano, (Université de Montpellier, FRANCE) and Prof. Patrik Johansson (Chalmers University of Technology, SWEDEN). The image represents the in situ spectro‐electrochemical cell used for the study of a lithium–sulfur battery for automotive applications by confocal Raman spectroscopy. This study allowed the identification of the polysulfides formed in the electrolyte. Read the full text of the article at 10.1002/cphc.201500448
“Precision” drug development?
Authors: Woodcock J
Published: September 2015

The concept of precision medicine has entered broad public consciousness, spurred by a string of targeted drug approvals, highlighted by the availability of personal gene sequences, and accompanied by some remarkable claims about the future of medicine. It is likely that precision medicines will require precision drug development programs. What might such programs look like?
A Key concept in Magnesium Secondary Battery Electrolytes
Authors: Bertasi Federico , Hettige Chaminda , Sepehr Fatemeh , Bogle Xavier , Pagot Gioele , Vezzù Keti , Negro Enrico , Paddison Stephen J. , Greenbaum Steve G. , Vittadello Michele , Di Noto Vito
Published: September 2015

A critical roadblock toward practical Mg‐based energy storage technologies is the lack of reversible electrolytes that are safe and electrochemically stable. Here, we report on high‐performance electrolytes based on 1‐ethyl‐3‐methylimidazolium chloride (EMImCl) doped with AlCl3 and highly amorphous δ‐MgCl2. The phase diagram of the electrolytes reveals the presence of four thermal transitions that strongly depend on salt content. High‐level density functional theory (DFT)‐based electronic structure calculations substantiate the structural and vibrational assignment of the coordination complexes. A 3D chloride‐concatenated dynamic network model accounts for the outstanding redox behaviour and the electric and magnetic properties, providing insight into the conduction mechanism of the electrolytes. Mg anode cells assembled using the electrolytes were cyclically discharged at a high rate (35 mA g−1), exhibiting an initial capacity of 80 mA h g−1 and a steady‐state voltage of 2.3 V.
How validated receptor occupancy flow cytometry assays can impact decisions and support drug development
Authors: Moulard Maxime , Ozoux Marie‐Laure
Published: September 2015

Because of the pressure of significant attrition in drug development, demonstration of target engagement after drug administration enables dose and regimen optimization, patient selection, and stratification from the earliest stages of drug development. The determination of receptor occupancy (RO) can support these efforts. Flow cytometry is one of the preferred technologies to be used based on the important advances in the technology over the last years enabling the simultaneous determination on target cells, of multi intra or surface cell parameters with adequate precision in a regulated environment. Nevertheless, compared to other platforms using the same antigen–antibody binding concept, the flow cytometry approach has faced several challenges, not only due to the technology per se and the diversity of receptor occupancy approaches, but also related to the nature of the matrix where the determination is performed.

To illustrate these points, three case studies (antibody–drug conjugate and naked antibody) are provided here to highlight the importance of the choice of the right antibody pair to measure both receptor density (RD) and occupancy by the drug on cancer cells in blood and in bone marrow and the possibility to circumvent the lack of a critical reagent with an innovative approach. In addition, the use of RO data to determine the minimum anticipated biological effect level (MABEL) with translational data from preclinical to human studies, selection of starting dose for the first in man study will be discussed. © 2015 International Clinical Cytometry Society
Disposition of isoflupredone acetate in plasma, urine and synovial fluid following intra‐articular administration to exercised Thoroughbred horses
Authors: Knych Heather K. , Harrison Linda M. , White Alexandria , McKemie Daniel S.
Published: September 2015

The use of isoflupredone acetate in performance horses and the scarcity of published pharmacokinetic data necessitate further study. The objective of the current study was to describe the plasma pharmacokinetics of isoflupredone acetate as well as time‐related urine and synovial fluid concentrations following intra‐articular administration to horses. Twelve racing‐fit adult Thoroughbred horses received a single intra‐articular administration (8 mg) of isoflupredone acetate into the right antebrachiocarpal joint. Blood, urine and synovial fluid samples were collected prior to and at various times up to 28 days post drug administration. All samples were analyzed using liquid chromatography‐Mass Spectrometry. Plasma data were analyzed using a population pharmacokinetic compartmental model. Maximum measured plasma isoflupredone concentrations were 1.76 ± 0.526 ng/mL at 4.0 ± 1.31 h and 1.63 ± 0.243 ng/mL at 4.75 ± 0.5 h, respectively, for horses that had synovial fluid collected and for those that did not. The plasma beta half‐life was 24.2 h. Isoflupredone concentrations were below the limit of detection in all horses by 48 h and 7 days in plasma and urine, respectively. Isoflupredone was detected in the right antebrachiocarpal and middle carpal joints for 8.38 ± 5.21 and 2.38 ± 0.52 days, respectively. Results of this study provide information that can be used to regulate the use of intra‐articular isoflupredone in the horse. Copyright © 2015 John Wiley & Sons, Ltd.
Cre recombinase activity is inhibited in vivo but not ex vivo by a mutation in the asymmetric spacer region of the distal loxP site
Authors: Arguello Tania , Moraes Carlos T.
Published: September 2015

The cre/loxP recombination system is a valuable tool used to generate tissue specific genomic rearrangements in mouse models. The deletion of a region of interest flanked by two loxP sites is accomplished by the recombinase (cre) enzyme, which binds to the inverted repeat segments of two loxP sites and recognition of a conserved TA sequence in the asymmetric central spacer region “ATAACTTCGTATA ‐NNNTANNN‐TATACGAAGTTAT. In vivo, we found that a single T to C mutation at position 4 of the central spacer region in the distal (3′) loxP site, completely inhibited the recombination reaction in two conditional mouse models. These mice were generated using a mitochondrial methionyl‐tRNA formyltransferase (Mtfmt) gene targeted construct and cre transgene under the control of tissue‐specific promoters: calcium/calmodulin‐dependent kinase II alpha (Camk2a‐cre) and myosin light polypeptide 1 (Myl1‐cre). Surprisingly, transient transfection of a plasmid expressing cre in dermal fibroblasts derived from the same mutant floxed Mtfmt(loxP/loxP) mice line, successfully deleted the region of interest. This study demonstrates the sequence specificity required in vivo, the possibility of bypassing this limitation by expressing high levels of cre recombinase ex vivo and raises concerns related to the quality control of large scale production of gene targeted constructs and mice. genesis 53:695–700, 2015. © 2015 Wiley Periodicals, Inc.
Queen execution increases relatedness among workers of the invasive Argentine ant,Linepithema humile
Authors: Inoue Maki N. , Ito Fuminori , Goka Koichi
Published: September 2015

Polygyny in social insects can greatly reduce within‐nest genetic relatedness. In polygynous ant species, potential rival queens in colonies with multiple queens are often executed by other queens, workers, or both. The Argentine ant,Linepithema humile, native to South America, forms a “supercolony” that is composed of a large number of nests and is considered to contribute to the ant's invasion success. Currently, four mutually antagonistic supercolonies are contiguously distributed within a small area of Japan. Here, we analyzed the genetic structure and relatedness within and among the four supercolonies using microsatellite markers to clarify howL. humilemaintains its supercoloniality. The results ofAMOVAandBASP, theFSTvalues, and the existence of several private alleles indicated that theL. humilepopulation in the Kobe area had a characteristic genetic structure. Within a given supercolony, there was significant genetic differentiation (FST) among workers collected in May and those collected in September. The significant deviation from Hardy–Weinberg equilibrium increased, and the relatedness among workers significantly increased from May to September in all supercolonies. This result suggested that the supercolonies replaced old queens with new ones during the reproductive season, thus supporting the plausibility of queen execution. From the perspective of kin selection, workers collectively eliminate queens, thereby increasing their own inclusive fitness. Restricted gene flow among supercolonies, together with mating with sib and queen execution, could help to maintain the unique social structure ofL. humile, the distribution of which is expanding worldwide.
A quantitative assessment on the response of flow regimes to cumulative forest disturbances in large snow‐dominated watersheds in the interior of British Columbia, Canada
Authors: Zhang Mingfang , Wei Xiaohua , Li Qiang
Published: September 2015

Frequent forest disturbances can significantly affect flow regimes (magnitude, timing, frequency, duration, and variability) and associated aquatic ecological functions. However, the lack of a comprehensive understanding of the impacts of forest disturbances on flow regimes impedes the development of adaptive strategies for sustainable water resource management and ecosystem protection. In this study, an innovative methodology that combines the time series cross‐correlation analysis and paired‐year approach was developed and applied in two snow‐dominated large watersheds (the Baker Creek and Willow River watersheds in the central interior of British Columbia (BC)) to provide a quantitative assessment on how forest disturbances affect the components of flow regimes at a large watershed scale. The results showed that the magnitude, variability, and return period of high flows in the Baker Creek watershed were increased on average by 154.3%, 324.2%, and 11 years, respectively, and the timing of high flows was advanced by about 9 days during the disturbed periods. In contrast, forest disturbances caused only a 36.2% increment in the magnitude and a 4‐day increase in the duration of high flows in the Willow River watershed. The responses of low flow regimes were less sensitive than those of high flow regimes. Only the magnitude and variability of low flows in the Baker Creek watershed and the duration of low flows in the Willow River watershed were significantly altered by forest disturbances. These findings can have implications for water management and ecosystem protection in the context of growing anthropogenic disturbances. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.
Nickel‐Molybdenum and Nickel‐Tungsten Dithiolates: Hybrid Models for Hydrogenases and Hydrodesulfurization
Authors: Schilter David , Fuller Amy L. , Gray Danielle L.
Published: September 2015

The heterobimetallic complexes [(dppe)Ni(pdt)Mo(CO)4], [(dcpe)Ni(pdt)Mo(CO)4], [(dppe)Ni(pdt)W(CO)4] and [(dcpe)Ni(pdt)W(CO)4] {dppe = Ph2P(CH2)2PPh2; dcpe = Cy2P(CH2)2PCy2; pdt2– = –S(CH2)3S–} have been prepared and structurally characterized. The internuclear separation in these NiIIM0 species is highly sensitive to diphosphine basicity and is smallest in the dppe complexes wherein the planar Ni centres are electron‐poor and require interaction with the group 6 metal. The NiIIW0 species [(dppe)Ni(pdt)W(CO)4] was converted into its stable conjugate acid [(dppe)Ni(pdt)HW(CO)4]+, a rare example of a nickel–tungsten hydride. This NiIIHWII complex is an electrocatalyst for H+ reduction and is relevant to both biological and synthetic H2‐processing catalysts.
Cytotoxicity and Structural Analyses of 2,2′‐Bipyridine‐, 4,4′‐Dimethyl‐2,2′‐bipyr­idine‐ and 2‐(2′‐Pyridyl)quinoxalineplatinum(II) Complexes
Authors: Pages Benjamin J. , Zhang Yingjie , Li Feng , Sakoff Jennette , Gilbert Jayne , Aldrich‐Wright Janice R.
Published: September 2015

Invited for the cover of this issue is the group of Janice Aldrich‐Wright at the University of Western Sydney, Australia. The cover image shows X‐ray crystal structures and CD spectra of platinum(II) complexes of 4,4'‐dimethyl‐2,2'‐bipyridine and 2‐(2'‐pyridyl)quinoxaline against a background of fluorescently stained HT29 human colon carcinoma cells. The Southern Cross refers to the country of origin of this work.
Exploring the Chemistry of Furans: Synthesis of Functionalized Bis(furan‐2‐yl)methanes and 1,6‐Dihydropyridazines
Authors: Lopes Susana M. M. , Henriques Marta S. C. , Paixão José A. , Pinho e Melo Teresa M. V. D.
Published: September 2015

The reactivity of 2,2‐bis(furan‐2‐yl)propane towards nitroso‐ and azoalkenes was explored. The expected hetero‐Diels–Alder adducts, 4a,7a‐dihydro‐4H‐furo[2,3‐e][1,2]oxazines and 4a,7a‐dihydrofuro[3,2‐c]pyridazines, were obtained in good yield. The furo‐oxazines were easily converted into the corresponding bis(furan‐2‐yl)methanes bearing an open‐chain oxime. Interestingly, the synthesized furo‐pyridazines showed a different chemical behavior. In the presence of HCl, they underwent a rearrangement giving 6‐(2‐oxobutyl)‐1,6‐dihydropyridazine derivatives in a process having as its key step a furan ring‐opening reaction. The synthesis of 4a,7a‐dihydrofuro[3,2‐c]pyridazines from 2‐methylfuran and the subsequent acid‐catalysed rearrangement to the corresponding 6‐(2‐oxopropyl)‐1,6‐dihydropyridazines was also achieved.
Principal Components – Based Techniques in Voltammetric Determination of Caffeic, Syringic and Vanillic Acids
Authors: Ciepiela Filip , Sordoń Wanda , Jakubowska Małgorzata
Published: September 2015

It was demonstrated that Principal Components Analysis and Principal Components Regression support qualitative and quantitative investigation of three‐component synthetic samples containing micromolar concentration of caffeic acid (CA), syringic acid (SA) and vanillic acid (VA), in various proportions. The first, second and third PCs enable modelling of relationships and distinction of objects of different composition. Optimized and validated multivariate calibration models, implemented on the basis of the samples selected with the help of 3‐level full factorial design, effectively support simultaneous determination of the considered analytes. Obtained RMSEP was no higher than 0.23 μm for CA, 0.17 μm for SA and 0.21 μm for VA, in relation to the concentration of 1.9 to 21.4 μm of each compound. Recovery between 90–108% for considered analytes, determined in synthetic wine solution, was additional verification of calibration model. Application of automatic baseline correction was extensively studied.
Proteome analysis of testis from infertile protein C inhibitor‐deficient mice reveals novel changes in serpin processing and prostaglandin metabolism
Authors: Yang Hanjiang , Wahlmüller Felix Christof , Uhrin Pavel , Baumgartner Roland , Mitulovic Goran , Sarg Bettina , Geiger Margarethe , Zellner Maria
Published: September 2015

Serine protease inhibitors (serpin) have therapeutic potential in a variety of pathogenic processes, ranging from thrombosis and altered immune response to liver cirrhosis. To investigate the physiological effects of protein C inhibitor (PCI, serpinA5), its gene was inactivated in a mouse model, resulting in male infertility. In the present report, 2D differential gel electrophoresis was utilized to investigate the molecular mechanisms for PCI involvement in male reproduction. Comparing the testes proteomes of three PCI‐knockout mice with three wild types demonstrated similar patterns with the exception of a massive upregulation of prostaglandin reductase 1 (tenfold; p < 0.002) and the complete shifts in the molecular weights of serpinA1C and serpinA3K. All these PCI‐dependent proteome changes were immunologically verified. Unbiased proteome analysis indicated that inactivation of serpinA5 strongly influenced both the protein species pattern of other A‐clade serpins as well as prostaglandin metabolism in the testes.
Humoral response against sialyl‐Lea glycosylated protein species in esophageal cancer: Insights for immunoproteomic studies
Authors: Fernandes Elisabete , Peixoto Andreia , Neves Manuel , Afonso Luís Pedro , Santos Lúcio Lara , Ferreira José Alexandre
Published: September 2015

Esophageal cancers (ECs) show poor prognosis and decreased overall survival due to late diagnosis and ineffective therapeutics, urging the introduction of novel biomarkers to aid disease management. The levels of sialyl‐Lewis(a) antigen (sLea) are frequently increased in digestive tumours, which has been explored in serological non‐invasive prognostication (CA19‐9 test); however, with low sensitivity and specificity. Autoantibodies against cancer antigens are considered the next generation biomarkers, as they are present in circulation long before tumour‐associated proteins. Based on these observations we have mined the serum of EC patients (n = 7) for antibodies against sLea‐glycosylated protein species. All EC were positive for sLea, irrespectively of their histological nature but only two patients showed elevated CA19‐9. Moreover, IgG titers, with emphasis on IgG1, were elevated in EC patients in comparison to the control group. SLea‐glycoproteins were then extracted from tumours of patients with negative CA19‐9, isolated by immunoprecipitation and blotted with patients IgG. Autoantibodies against sLea‐glycosylated proteins were detected in all cases. Different SLea‐glycoproteins were observed for tumours of distinct histological natures, which now require identification and validation in larger patient sets. This preliminary data suggests that antoantibodies against sLea glycosylated proteins hold potential for non‐invasive diagnosis in CA19‐9 negative cases and sets the rational for future immunoproteomic studies envisaging highly specific EC biomarkers.
Fuel briquettes from food‐processing sludge
Authors: Chiou Ing‐Jia , Chen Ching‐Ho , Liu Wei‐Lin , Wu I‐Tsung
Published: September 2015

Food‐processing sludge (FPSs) have high moisture content (approximately 80–90%) and odor, and therefore can easily become a potential environmental hazard. However, FPS has a higher calorific value and a lower ash content (dry basis). This study assessed the fuel briquettes potential of different food‐processing sludge‐derived fuels (FPSDFs) through analysis of their FPSs composition and combustion characteristics. The experimental results showed that FPSs were weak acid with high concentrations of chloride ions. Moreover, the calorific value of FPSs (18.59–25.70 MJ/kg, dry basis) could reach up to 72.4–100.1% of that of coal. The formability of FPSDFs was significantly related to FPSs type, and FPSDFs were characterized by high temperature (900–1100°C), flammability, low‐moisture regain (8–14%) and lightweight (0.7–0.9 g/cm3, dry basis). Considering fuel potential revealed that FPSs from the dairy and beverage industries was the most suitable material for manufacturing fuel. © 2015 American Institute of Chemical Engineers Environ Prog, 34: 1790–1795, 2015
Preparation of triethylenetetramine‐modified zirconosilicate molecular sieve for carbon dioxide adsorption
Authors: Yang Fan‐Ming , Chen Lang , Au Chak‐Tong , Yin Shuang‐Feng
Published: September 2015

Mesoporous molecular sieve Zr‐MCM‐41 was modified with triethylenetetramine (TETA) and tested for carbon dioxide (CO2) adsorption for the first time. The adsorbent was characterized by powder X‐ray diffraction, N2 adsorption‐desorption, energy dispersive spectrometer, Fourier transform‐infrared spectroscopy, thermogravimetric analysis, and temperature‐programmed desorption of CO2 and NH3. A maximum CO2 adsorption capacity of 3.36 mmol g−1 at 50°C in a stream of 5% CO2 concentration was obtained, which is 2.7 times that of TETA‐functionalized MCM‐41. The TETA‐modified Zr‐MCM‐41 is 30°C higher than the TETA‐modified MCM‐41 in terms of thermal stability. We find that the former adsorbent is superior in reusability. It is envisaged that the adsorbent is applicable in CO2 capture. © 2015 American Institute of Chemical Engineers Environ Prog, 34: 1814–1821, 2015