bluuebunny/crossref_metadata_2025 huggingface dataset:
Professional Competencies for Student Affairs Practice
Authors: Munsch Patty , Cortez Lori
Published: June 2014

The purpose of this chapter is to explore the integration of the ACPA/NASPA Professional Competency Areas for Student Affairs Practitioners (ACPA/NASPA, 2010) on community college campuses. The competencies provide specific skill sets for a broad range of student affairs practice areas that should be met by professionals throughout their careers. These competencies provide a tool to help assess and support staff development, and create clear performance expectations.
Facile Synthesis of Porous Zn2Ti3O8 Nanorods for Photocatalytic Overall Water Splitting
Authors: Qu Yang , Zhou Wei , Ren Zhiyu , Wang Guofeng , Jiang Baojiang , Fu Honggang
Published: June 2014

Metastable‐phase porous Zn2Ti3O8 nanorods as photocatalysts for overall water splitting, coupled with RuO2 as co‐catalysts, were synthesized by using ethylene glycol as a phase‐stabilizing and 1 D structure‐directing agent. The typical electronic energy band gap of Zn2Ti3O8 was confirmed to be excellent for overall water splitting photocatalysts by theoretical calculations and experimental results. Steady and stoichiometric H2 and O2 evolutions were observed, which increased with time. The yields of H2 and O2 were near to 4 and 2 μmol h−1 (0.1 g), respectively. The excellent overall water‐splitting activities could be attributed to the pure metastable phase of Zn2Ti3O8 possessing a suitable band gap and the porous 1 D structure favoring acceleration of the photogenerated charge transportation and separation.
Use of Thienylenevinylene and Ethynyl Molecular Bridges in Organic Dyes for Dye‐Sensitized Solar Cells: Implications for Device Performance
Authors: Pellejà Laia , Dominguez Rocío , Aljarilla Ana , Clifford John N. , de la Cruz Pilar , Langa Fernando , Palomares Emilio
Published: June 2014

The synthesis, full characterization, and use of a series of organic dyes with thienylenevinylene and ethynyl bridges as light‐harvesting chromophores in TiO2‐based photoelectrochemical dye‐sensitized solar cells are described. A maximum light‐to‐energy conversion efficiency of η=5.47 % under standard conditions is obtained for the organic dye denoted as FL16, which consists of an N,N‐bis(4‐hexyloxyphenyl)aniline donor moiety, an ethynylthieno[3,2‐b]thiophene π bridge, and a 2‐cyanoacrylic acid acceptor group. The device properties are investigated by charge extraction and transient photovoltage measurements.
Sign Reversal of a Large Circularly Polarized Luminescence Signal by the Twisting Motion of a Bidentate Ligand
Authors: Yuasa Junpei , Ueno Hiroshi , Kawai Tsuyoshi
Published: June 2014

This work demonstrates sign reversal of large circularly polarized luminescence (CPL) signal based on the hinge‐like twisting motion of a bidentate ligand, 3,3‐bis(diphenylphosphoryl)‐2,2‐bipyridine (BIPYPO), in a cis–trans isomerization of chiral europium(III) complexes. X‐ray diffraction analysis revealed that twisting motion of BIPYPO provides s‐cis and s‐trans geometries of a chiral EuIII complex containing either tris[3‐(trifluoromethylhydroxymethylene)‐(+)‐camphorate] (D‐1) or tris[3‐(heptafluoropropylhydroxymethylene)‐(+)‐camphorate] (D‐2). The s‐cis EuIII complexes show eight‐coordinate geometry around the EuIII ion, in which the chelate between the phosphoryl oxygen and the EuIII ion forces the s‐cis geometry of BIPYPO. In contrast, the phosphorus–nitrogen interaction provides a conformational lock for the s‐trans geometry of the BIPYPO ligand, inducing a quasi‐seven‐coordinate EuIII complex. The difference in coordination geometry causes the sign change of the CPL signals between the s‐cis and s‐trans isomers, whereby the s‐cis and s‐trans isomers of EuIII complexes exhibit the positive and negative CPL signals, respectively, for the 5D0→7F1 transition. The proportion of the s‐trans‐D‐1 against s‐cis‐D‐1 increases upon changing the solvent from [D3]acetonitrile to [D6]acetone, inducing a sign change of the CPL signals. The complexes D‐1 and D‐2 show a biexponential decay with two different lifetimes, suggesting two emitting species, that is, the s‐cis and s‐trans isomers of EuIII complexes. In both cases, the proportions of the longer lifetime components (τ1) decrease and instead the shorter lifetime components (τ2) increase upon changing the solvent from [D3]acetonitrile to [D6]acetone.
Construction of Two‐Dimensional MoS2/CdS p–n Nanohybrids for Highly Efficient Photocatalytic Hydrogen Evolution
Authors: Zhang Jian , Zhu Zhenping , Feng Xinliang
Published: June 2014

2D MoS2 nanosheets have been utilized to fabricate 2D MoS2/CdS p–n nanohybrids through a one‐pot solvothermal process. Due to the unique p–n junction heterostructure, large specific surface area, and decreased band gap, MoS2/CdS nanohybrids manifested a superior H2‐production rate of ∼137 μmol h−1 under visible‐light irradiation and an apparent quantum yield of 10.5 % at 450 nm.
Triazole‐Assisted Ruthenium‐Catalyzed CH Arylation of Aromatic Amides
Authors: Al Mamari Hamad H. , Diers Emelyne , Ackermann Lutz
Published: June 2014

Site‐selective ruthenium(II)‐catalyzed direct arylation of amides was achieved through CH cleavages with modular auxiliaries, derived from easily accessible 1,2,3‐triazoles. The triazolyldimethylmethyl (TAM) bidentate directing group was prepared in a highly modular fashion through copper(I)‐catalyzed 1,3‐dipolar cycloaddition and allowed for ruthenium‐catalyzed CH arylations on arenes and heteroarenes, as well as alkenes, by using easy‐to‐handle aryl bromides as the arylating reagents. The triazole‐assisted CH activation strategy was found to be widely applicable, to occur under mild reaction conditions, and the catalytic system was tolerant of important electrophilic functionalities. Notably, the flexible triazole‐based auxiliary proved to be a more potent directing group for the optimized ruthenium(II)‐catalyzed direct arylations, compared with pyridyl‐substituted amides or substrates derived from 8‐aminoquinoline.
Supramolecularly Knitted Tethered Oligopeptide/Single‐Walled Carbon Nanotube Organogels
Authors: Zou Jiong , He Xun , Fan Jingwei , Raymond Jeffery E. , Wooley Karen L.
Published: June 2014

A facile polymerization of an allyl‐functionalized N‐carboxyanhydride (NCA) monomer is utilized to construct an A‐B‐A‐type triblock structure containing β‐sheet‐rich oligomeric peptide segments tethered by a poly(ethylene oxide) chain, which are capable of dispersing and gelating single‐walled carbon nanotubes (SWCNTs) noncovalently in organic solvents, resulting in significant enhancement of the mechanical properties of polypeptide‐based organogels.
Taming the Carboxyl Group for Directed Carbometalation: Observations on the Use of Anions, Dianions and Ester Enolates
Authors: Desrat Sandy , Gray Philip J. , Penny Matthew R. , Motherwell William B.
Published: June 2014

Carboxylate anions, dianions and ester enolates provide simultaneous protection and activation for directed carbometalation reactions. Advantage can be taken of the bis‐carbanionic character of the intermediate for further controlled CC bond forming reactions.
Noncanonical DNA Secondary Structures as Drug Targets: the Prospect of the i‐Motif
Authors: Amato Jussara , Iaccarino Nunzia , Randazzo Antonio , Novellino Ettore , Pagano Bruno
Published: June 2014

Under certain conditions, specific DNA sequences have the potential to adopt noncanonical secondary structures, such as i‐motifs. Interestingly, these DNA stretches are not randomly located throughout the genome but rather frequently clustered in regulatory regions of oncogenes and in telomeres, the terminal regions of chromosomes. Recent evidences suggest that i‐motif DNA structures exist in living cells and could be involved in a variety of biological processes, such as replication, regulation of oncogene expression, and telomere functions. Therefore, the targeting of i‐motif DNA is an emerging research area in medicinal chemistry. Bringing these noncanonical structures into focus as targets for anticancer drug design and gene regulation processes could be crucial for a better understanding of their biological functions and to open the way to new, effective strategies for cancer treatment.
Pharmacokinetics of single and repeat doses of icatibant
Authors: Leach J. Kevin , Spencer Kelly , Mascelli Maryann , McCauley Thomas G.
Published: June 2014

Purpose

Icatibant is a bradykinin‐2 receptor antagonist approved to treat acute hereditary angioedema attacks in adults. To‐date, no thorough investigation of the clinical pharmacokinetic (PK) parameters of icatibant and its primary metabolites has been reported. Here we present the PK results of two phase I clinical studies of icatibant in healthy human volunteers.

Methods

Single‐ and multiple‐dose plasma pharmacokinetics of icatibant were characterized in healthy volunteers. Icatibant concentration‐time profiles and PK parameters were derived after a single 30‐ or 90‐mg dose or three 30‐mg doses given at 6‐hour intervals.

Results

Maximal plasma concentrations for the 30‐mg (979 ± 262 ng/mL) and 90‐mg doses (2,719 ± 666 ng/mL) were achieved at <1 hour postdose. The total plasma icatibant exposure for the 30‐ and 90‐mg doses was 2,191 ± 565 and 6,736 ± 1,230 h · ng/mL, respectively, with elimination half‐life values of 1.48 ± 0.35 and 2.00 ± 0.57 hours, respectively.

Conclusions

Single 30‐ and 90‐mg subcutaneous administration of icatibant exhibited dose‐proportional PK with no appreciable accumulation upon repeated 30‐mg doses administered at 6‐hour intervals.
Nitrogen‐Doped Ordered Mesoporous Carbon with a High Surface Area, Synthesized through Organic–Inorganic Coassembly, and Its Application in Supercapacitors
Authors: Song Yanfang , Li Li , Wang Yonggang , Wang Congxiao , Guo Zaipin , Xia Yongyao
Published: June 2014

A new nitrogen‐doped ordered mesoporous carbon (N‐doped OMC) is synthesized by using an organic–inorganic coassembly method, in which resol is used as the carbon precursor, dicyandiamide as the nitrogen precursor, silicate oligomers as the inorganic precursors, and F127 as the soft template. The N‐doped OMC possesses a surface area as high as 1374 m2 g−1 and a large pore size of 7.4 nm. As an electrode material for supercapacitors, the obtained carbon exhibits excellent cycling stability and delivers a reversible specific capacitance as high as 308 F g−1 in 1 mol L−1 H2SO4 aqueous electrolyte, of which 58 % of the capacity is due to pseudo‐capacitance. The large specific capacitance is attributed to proper pore size distributions, large surface area, and high nitrogen content.
The Nature of One‐Dimensional Carbon: Polyynic versus Cumulenic
Authors: Neiss Christian , Trushin Egor , Görling Andreas
Published: June 2014

A question of both fundamental as well as practical importance is the nature of one‐dimensional carbon, in particular whether a one‐dimensional carbon allotrope is polyynic or cumulenic, that is, whether bond‐length alternation occurs or not. By combining the concept of aromaticity and antiaromaticity with the rule of Peierls distortion, the occurrence and magnitude of bond‐length alternation in carbon chains with periodic boundary conditions and corresponding carbon rings as a function of the chain or ring length can be explained. The electronic properties of one‐dimensional carbon depend crucially on the bond‐length alternation. Whereas it is generally accepted that carbon chains in the limit of infinite length have a polyynic structure at the minimum of the potential energy surface with bond‐length alternation, we show here that zero‐point vibrations lead to an effective equalization of all carbon–carbon bond lengths and thus to a cumulenic structure.
Toward Tunable Immobilized Molecular Catalysts: Functionalizing the Methylene Bridge of Bis(N‐heterocyclic carbene) Ligands
Authors: Zhong Rui , Pöthig Alexander , Haslinger Stefan , Hofmann Benjamin , Raudaschl‐Sieber Gabriele , Herdtweck Eberhardt , Herrmann Wolfgang A. , Kühn Fritz E.
Published: June 2014

A new immobilization mode for methylene‐bridged bis(NHC) (NHC=N‐heterocyclic carbene) ligand systems is presented, allowing fine‐tuning of the steric and electronic properties of the bidentate ligand. For example, four hydroxymethyl‐functionalized imidazolium salts (1 a–c and 2 a) and three bis(NHC) Pd complexes 3 a, 3 b, and 4 a are described. The chloro‐functionalized bis(NHC) Pd complex 4 a was obtained quantitatively by conversion of the hydroxyl substituent of complex 3 a into a chloro substituent by employing thionyl chloride. All three bis(NHC) complexes 3 a, 3 b, and 4 a were characterized by NMR spectroscopy, elemental analysis, mass spectrometry, and single‐crystal X‐ray diffraction. Two different synthetic routes were applied to immobilize the bis(NHC) Pd complex 3 a on polystyrene. The obtained heterogeneous catalyst 5 b was utilized for Suzuki–Miyaura cross‐coupling reactions and could be recycled without significant activity loss in four runs. Furthermore, the water‐soluble homogeneous catalyst 3 a itself could be employed for Suzuki–Miyaura cross‐coupling reactions in water.
Prioritizing Practice in Ombudsman and ADR Programs
Authors: Michael David E.
Published: June 2014

This article examines ways in which the Office of the Ombudsman/Center for Cooperative Resolution (OO/CCR) at the National Institutes of Health pursues activities that comprise an orientation toward practice and supports development of an “activist” ombudsman orientation. The article opens by describing challenges that alternative dispute resolution (ADR) organizations face, contrasts them with the experience of OO/CCR, details elements of a practice orientation as experienced at OO/CCR, and suggests ways in which ADR and ombudsman organizations may address their own challenges and pursue a practice orientation.
Visible‐Light‐Enhanced Electrocatalysis and Bioelectrocatalysis Coupled in a Miniature Glucose/Air Biofuel Cell
Authors: Zhang Lingling , Xu Zhikun , Lou Baohua , Han Lei , Zhang Xiaowei , Dong Shaojun
Published: June 2014

A glucose/air biofuel cell (BFC) that can convert both chemical and light energy into electricity is described. Polyterthiophene (pTTh), a photoresponsive conducting polymer, serves as cathode and catalyzes the reduction of oxygen. Taking advantage of the good environmental stability and exceptional optical properties of pTTh, the assembled BFC exhibits excellent stability and a fast photoresponse with an open‐circuit voltage (Voc) of 0.50 V and a maximum power output density (Pmax) of 23.65 μW cm−2 upon illumination by visible light of 10 mW cm−2, which is an enhancement of ca. 22 times as compared to Pmax in the dark. Additionally, we propose a possible mechanism for this enhancement. Fabricating a BFC in this manner provides an energy conversion model that offers high efficiency at low cost, paving an avenue for practical solar energy conversion on a large scale.
Looking to the eyes influences the processing of emotion on face‐sensitive event‐related potentials in 7‐month‐old infants
Authors: Vanderwert Ross E. , Westerlund Alissa , Montoya Lina , McCormick Sarah A. , Miguel Helga O. , Nelson Charles A.
Published: June 2014

Previous studies in infants have shown that face‐sensitive components of the ongoing electroencephalogram (the event‐related potential, or ERP) are larger in amplitude to negative emotions (e.g., fear, anger) versus positive emotions (e.g., happy). However, it is still unclear whether the negative emotions linked with the face or the negative emotions alone contribute to these amplitude differences. We simultaneously recorded infant looking behaviors (via eye‐tracking) and face‐sensitive ERPs while 7‐month‐old infants viewed human faces or animals displaying happy, fear, or angry expressions. We observed that the amplitude of the N290 was greater (i.e., more negative) to angry animals compared to happy or fearful animals; no such differences were obtained for human faces. Eye‐tracking data highlighted the importance of the eye region in processing emotional human faces. Infants that spent more time looking to the eye region of human faces showing fearful or angry expressions had greater N290 or P400 amplitudes, respectively. © 2014 Wiley Periodicals, Inc. Develop Neurobiol 75: 1154–1163, 2015
Investigating the influence of two different flow routing algorithms on soil–water–vegetation interactions using the dynamic ecosystem model LPJ‐GUESS
Authors: Tang Jing , Miller Paul A. , Crill Patrick M. , Olin Stefan , Pilesjö Petter
Published: June 2014

This paper compares two flow routing algorithms' influences on ecohydrological estimations in a northern peatland catchment, within the framework of an arctic‐enabled version of the dynamic ecosystem model LPJ‐GUESS. Accurate hydrological estimations are needed to fully capture vegetation dynamics and carbon fluxes in the subarctic peatland enviroment. A previously proposed distributed hydrological method based on the single flow (SF) algorithm extracted topographic indices has shown to improve runoff estimations in LPJ‐GUESS. This paper investigates model performance differences caused by two flow routing algorithms, and importantly both permafrost processes and peatland hydrology are included in the model. The newly developed triangular form‐based multiple flow (TFM) is selected due to its improved consideration of flow continuity and more realistic flow estimation over flat surfaces. A variety of measured data is included to assess both hydrological and ecological accuracy, and the results demonstrate that the choice of flow algorithm does matter for mesoscale ecohydrology applications. The allowance of flow convergence and consideration of flow partition differences from different terrain forms in the TFM algorithm yield better correspondence with the observed hydrological processes and also carbon fluxes. By directing flow to only one downslope cell together with its poorer depiction of flow over flat areas, the SF algorithm can result in too high runoff estimations for low‐flat regions and overestimate carbon uptake and release in the peatland. The results of this study also highlight the need for care when selecting flow routing algorithms for biogeochemical estimations, especially within hydrologically and climatically sensitive environments. Copyright © 2014 John Wiley & Sons, Ltd.
Application of central immunologic concepts to cancer: Helping T cells and B cells become intolerant of tumors
Authors: Anderson Colin C.
Published: June 2014

CD4‐mediated T‐cell help in the activation of CD8+ T cells and B cells, through linked‐recognition of antigenic determinants, is a long‐standing concept foundational to our understanding of immunity (presence of help) versus tolerance (lack of help). Surprisingly, this function of CD4+ T cells has not been extensively examined as a means to overcome immune tolerance of the self‐antigens made by tumor cells. Hesitation to employ this powerful mechanism may be due to the potential to cause unwanted autoimmune pathology. In this issue of the European Journal of Immunology, Snook et al. [Eur. J. Immunol. 2014. 44: 1956–1966] identify a state of split tolerance, showing that CD4+ T cells specific for a number of tumor‐associated self‐antigens are robustly tolerant, while their CD8+ T‐cell and B‐cell counterparts are far less tolerant. Furthermore, the authors demonstrate that provision of linked foreign helper epitopes, such as influenza hemagglutinin, substantially enhances both CD8+ T‐cell and B‐cell responses to tumor self‐antigens without causing any overt autoimmune pathology. These findings provide a strong rationale to employ foreign helper epitopes in cancer vaccines and highlight the need to fully explore therapeutic strategies that are based on well‐established immunologic concepts.
Hydrothermal Fabrication and Luminescence Properties of One‐Dimensional TiO2:Eu3+ Spindlelike Nanorods
Authors: Zhang Hongguang , Sheng Ye , Zheng Keyan , Zhou Xiuqing , Shi Zhan , Xu Xuechun , Zou Haifeng
Published: June 2014

Highly crystalline and uniform TiO2:Eu3+ spindlelike nanorods have been successfully synthesized through a facile hydrothermal route with citric acid (H3Cit) and ethanediamine (en) as the assistant agents for the first time. X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected‐area electron diffraction (SAED), and photoluminescence (PL) spectroscopy were utilized to characterize the samples. In the synthetic process, the dosages of ethanediamine and citric acid are important parameters that affect the morphology and size of the final products. A possible formation process of the samples has been proposed in detail. The existence of Eu3+ sites in the TiO2 nanorods was proved by site‐selective spectroscopy. Furthermore, the TiO2:Eu3+ spindlelike nanorods exhibit bright red (Eu3+, 5D0→7F2) luminescence under ultraviolet (UV) excitation; therefore, they may find potential applications in fluorescent lamps and field‐emission displays (FEDs).
Substitution‐Modulated Anticancer Activity of Half‐Sandwich Ruthenium(II) Complexes with Heterocyclic Ancillary Ligands
Authors: Mitra Raja , Samuelson Ashoka G.
Published: June 2014

Ten new organometallic half‐sandwich ruthenium complexes with heterocyclic ligands have been synthesized (H1–H10). The substituents on the ancillary heterocyclic ligands were varied to understand the effect of substitution on anticancer activity. The crystallographic characterization of five complexes confirms that they adopt “three‐legged piano‐stool” structures and are stabilized by intramolecular hydrogen bonding. Complexes H2 and H3 also exhibit halogen bonding in the solid state. In aqueous media, the complexes form dinuclear ruthenium species. Complex H1 with a noncytotoxic heterocycle, 6‐fluoro‐2‐mercaptobenzothiazole, and complex H11 with the unsubstituted 2‐mercaptobenzothiazole are the most active against A2780 and KB cell lines. The substitution of the H atoms on the ancillary ligand with Cl or Br atoms leads to a decrease in the anticancer activity. With the exception of fluorine‐substituted H5, the complexes with mercaptobenzoxazole (H6–H9) are inactive against all of the tested cell lines. Ruthenium complexes with mercaptonaphthimidazole (H10) and mercaptobenzimidazole (H13) do not show any anticancer activity. The active complexes show a biphasic melting curve when incubated with calf thymus (CT) DNA. These complexes only inhibit thioredoxin reductase (TrxR) enzyme activity to a small extent. The substitution of hydrogen atoms with fluorine atoms in the aromatic heterocyclic ligands on organometallic half‐sandwich ruthenium complexes has the most beneficial effect on their anticancer activity.
Self‐Assembly of Subnanometer‐Scaled Polyhedral Oligomeric Silsesquioxane (POSS) Macroions in Dilute Solution
Authors: Zhou Jing , Yin Panchao , Hu Lang , Haso Fadi , Liu Tianbo
Published: June 2014

Both positively and negatively charged polyhedral oligomeric silsesquioxane (POSS) electrolytes were observed to self‐assemble into blackberry‐type supramolecular structures in water/acetone mixed solvents, driven by the counterion‐mediated attraction. Laser light‐scattering studies reveal that the sizes of the blackberry structures increase with increasing acetone content, which suggests a charge‐regulated process. Studies on two oppositely charged POSS macroions with identical charges and similar sizes show the discrepancy between positively and negatively charged POSS macroions, which is related to counterions, ionic domains of macroions, and the water‐bridged hydrogen bonding between monomers. These POSS ions further decrease the lower size limit of macroions that can self‐assemble in polar solvents reported to date. The new phenomena were observed in the self‐assembly process of POSS macroions relative to other macroion systems.
Phosphate Diester Cleavage, DNA Interaction and Cytotoxic Activity of a Bimetallic Bis(1,4,7‐triazacyclononane) Zinc Complex
Authors: Montagner Diego , Gandin Valentina , Marzano Cristina , Erxleben Andrea
Published: June 2014

The dinuclear zinc complex [Zn2{bcmp(‐H)}(μ‐Cl)](ClO4)2·H2O {bcmp = 2,6‐bis(1,4,7‐triazacyclonon‐1‐ylmethyl)‐4‐methylphenol} has been synthesized and structurally characterized. The DNA binding affinity was assessed by ethidium bromide fluorescence quenching experiments. The complex relaxes supercoiled pUC19 DNA into the nicked form at low micromolar concentration. Mechanistic studies were carried out using the DNA and RNA models bis(2,4‐dinitrophenyl) phosphate (BDNPP) and 2‐hydroxypropyl p‐nitrophenyl phosphate (HPNP). A detailed kinetic analysis suggested that the bridging OH group of the solution species [Zn2{bcmp(‐H)}(μ‐OH)]2+ acts as the nucleophile in the hydrolysis of BDNPP, while in the case of HPNP, the bridging OH group acts as a general base and seems to shift to a terminal position upon substrate coordination. Finally, the cytotoxicity profile of the dinuclear zinc(II) complex was assessed. The complex showed promising in vitro antitumour activity against pancreatic and lung cancers cell lines.
Solid‐Phase Synthesis of Cyclic Lipopeptidotriazoles
Authors: Vilà Sílvia , Camó Cristina , Figueras Eduard , Badosa Esther , Montesinos Emilio , Planas Marta , Feliu Lidia
Published: June 2014

The solid‐phase synthesis of cyclic lipopeptidotriazoles derived from the cyclic decapeptide c(Lys‐Lys2‐Leu‐Lys‐Lys5‐Phe‐Lys‐Lys‐Leu‐Gln) (BPC194), incorporating a triazolyl ring at Lys2 and a hexanoyl group at Lys5, was studied. Four different strategies that required the use of five orthogonal protecting groups (Fmoc, tBu, All, pNZ, ivDde) were explored. The influence of the side‐chain protection of Lys2 and Lys5 with the ivDde and pNZ groups was evaluated by incorporating Lys2(ivDde)/Lys5(pNZ) or Lys2(pNZ)/Lys5(ivDde). The order of removal of these protecting groups and of the introduction of the hexanoyl and triazolyl moieties was also studied. The best strategy included: (i) synthesis of a cyclic peptidyl resin bearing Lys2(ivDde) and Lys5(pNZ); (ii) pNZ group removal; (iii) acylation with hexanoic acid; (iv) ivDde group removal; and (v) acylation with propiolic acid followed by an azide–alkyne 1,3‐dipolar cycloaddition. By using this protocol, a set of cyclic lipopeptidotriazoles was prepared in high purities.
The inner speech of behavioral regulation: Intentions and task performance strengthen when you talk to yourself as a You
Authors: Dolcos Sanda , Albarracin Dolores
Published: June 2014

People often talk to themselves using the first‐person pronoun (I), but they also talk to themselves as if they are speaking to someone else, using the second‐person pronoun (You). Yet, the relative behavioral control achieved by I and You self‐talk remains unknown. The current research was designed to examine the potential behavioral advantage of using You in self‐talk and the role of attitudes in this process. Three experiments compared the effects of I and You self‐talk on problem solving performance and behavioral intentions. Experiment 1 revealed that giving self‐advice about a hypothetical social situation using You yielded better anagram task performance than using I. Experiment 2 showed that using You self‐talk in preparation for an anagram task enhanced anagram performance and intentions to work on anagrams more than I self‐talk, and that these effects were mediated by participants' attitudes toward the task. Experiment 3 extended these findings to exercise intentions and highlighted the role of attitudes in this effect. Altogether, the current research showed that second‐person self‐talk strengthens both actual behavior performance and prospective behavioral intentions more than first‐person self‐talk. Copyright © 2014 John Wiley & Sons, Ltd.
Critical Quantitative Inquiry in Context
Authors: Stage Frances K. , Wells Ryan S.
Published: June 2014

This chapter briefly traces the development of the concept of critical quantitative inquiry, provides an expanded conceptualization of the tasks of critical quantitative research, offers theoretical explanation and justification for critical research using quantitative methods, and previews the work of quantitative criticalists presented in this volume.
Disrupting the Pipeline: Critical Analyses of Student Pathways Through Postsecondary STEM Education
Authors: Metcalf Heather E.
Published: June 2014

Critical mixed methods approaches allow us to reflect upon the ways in which we collect, measure, interpret, and analyze data, providing novel alternatives for quantitative analysis. For institutional researchers, whose work influences institutional policies, programs, and practices, the approach has the transformative ability to expose and create space for altering rather than reproducing problematic institutional stratifications and inequities. The usefulness of this approach is illustrated here using examples from a critical mixed methods study of student pathways through postsecondary STEM education.
Effect of acetabular cup design on metal ion release in two designs of metal‐on‐metal hip resurfacing
Authors: Cadossi Matteo , Tedesco Giuseppe , Savarino Lucia , Baldini Nicola , Mazzotti Antonio , Greco Michelina , Giannini Sandro
Published: June 2014

The purpose of this observational prospective cohort study was to evaluate the serum concentrations of cobalt (Co), chromium (Cr), and nickel (Ni) at a 2‐year follow‐up in patients operated on with a novel design of hip resurfacing: Romax resurfacing system (RRS). RRS is characterized by the presence of an acetabular notch which theoretically provides a wider range of motion and a reduced incidence of groin pain. The presence of radiolucencies and functional outcome, assessed using the Harris hip score (HHS) and the University of California Activity scale (UCLA), were secondary endpoints. Moreover, these results were compared with those obtained in our previous study from a similar cohort of patients implanted using the Birmingham Hip Resurfacing (BHR) system. At a 2‐year follow‐up, the serum levels of Co in patients operated on using the RRS were five times higher (p = 0.0002) than those found before surgery (Co, means: 1.04 and 0.20 ng/mL, respectively); similarly, Cr levels were 13 times higher (p < 0.0001) at a 2‐year follow‐up than before surgery (Cr, means: 1.69 and 0.13 ng/mL, respectively). Ni concentrations (0.42 and 0.78 ng/mL) were not significantly different (p = 0.16), even if they increased 86% after surgery. In the RRS patients, an inverse correlation was found between Co and Cr concentrations and length of follow‐up (Co: r = −0.64, p = 0.0096; Cr: r= −0.45, p = 0.08). The serum levels of Co and Cr were not significantly different between RRS (Co: 1.04 ng/mL and Cr: 1.69 ng/mL) and BHR (Co: 1.39 ng/mL and Cr: 2.30 ng/mL) patients at 2 years (p = 0.95 and 0.26 for Co and Cr, respectively). Our results showed that RRS patients achieved an excellent clinical outcome with limited metal ion release. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 1595–1601, 2014.
Association Between Global Biomarkers of Oxidative Stress and Hip Fracture in Postmenopausal Women: A Prospective Study
Authors: Yang Shuman , Feskanich Diane , Willett Walter C , Eliassen A Heather , Wu Tianying
Published: June 2014

Human studies suggest that oxidative stress is a risk factor for osteoporosis, but its relationship with fracture risk is poorly understood. The purpose of the present study was to investigate the association between biomarkers of oxidative stress and hip fracture in postmenopausal women. We conducted a prospective study in the Nurses' Health Study among 996 women aged 60 years or older at baseline blood collection in 1989–1990. Plasma fluorescent oxidation products (FlOPs) were measured at three excitation/emission wavelengths (360/420 nm named as FlOP_360; 320/420 nm named as FlOP_320; and 400/475 nm named as FlOP_400). FlOPs are generated from many different pathways (lipid, protein, and DNA) and reflect a global oxidation burden. FlOP assay is 10–100 times more sensitive than measurement of malondialdehyde. We used Cox proportional hazards regression model to investigate the association between baseline plasma FlOPs and the risk of hip fracture, adjusting for multiple hip fracture risk factors such as age, history of osteoporosis, history of hypertension, prior fracture, and smoking status. Forty-four hip fractures (4.4%) were identified during the follow-up (maximum = 23 years). In the multivariable model, the hazard ratios (HRs) of hip fracture in the second and third tertiles of FlOP_320 were 2.11 (95% confidence interval [CI] = 0.88–5.10) and 2.67 (95% CI = 1.14–6.27), respectively, in comparison with the lowest tertile, and the risk increased linearly with increasing FlOP_320 (p for trend = 0.021). Neither FlOP_360 nor FlOP_400 was significantly associated with risk of hip fracture (tertile 3 versus tertile 1: HR = 0.70, 95% CI = 0.32–1.54, p for trend = 0.386 for FlOP_360; and HR = 0.88, 95% CI = 0.40–1.96, p for trend = 0.900 for FlOP_400). In this prospective study, higher plasma FlOP_320 was an independent risk factor for hip fracture. Our results need further confirmation. © 2014 American Society for Bone and Mineral Research.
Ghrelin Augments the Expressions and Secretions of Proinflammatory Adipokines, VEGF120 and MCP‐1, in Differentiated 3T3‐L1 Adipocytes
Authors: Kitahara Atsuko , Takahashi Kazuto , Moriya Rie , Onuma Hirohisa , Handa Keiko , Sumitani Yoshikazu , Tanaka Toshiaki , Katsuta Hidenori , Nishida Susumu , Sakurai Takuya , Inukai Kouichi , Ohno Hideki , Ishida Hitoshi
Published: June 2014

Ghrelin is a physiological‐active peptide with growth hormone‐releasing activity, orexigenic activity, etc. In addition, the recent study has also suggested that ghrelin possesses the pathophysiological abilities related with type 2 diabetes. However, the ghrelin‐direct‐effects implicated in type 2 diabetes on peripheral tissues have been still unclear, whereas its actions on the central nervous system (CNS) appear to induce the development of diabetes. Thus, to assess its peripheral effects correlated with diabetes, we investigated the regulatory mechanisms about adipokines, which play a central role in inducing peripheral insulin resistance, secreted from mature 3T3‐L1 adipocytes stimulated with ghrelin in vitro .

The stimulation with 50 nmol/L ghrelin for 24 h resulted in the significant 1.9‐fold increase on vascular endothelial growth factor‐120 (VEGF120) releases (p < 0.01) and the 1.7‐fold on monocyte chemoattractant protein‐1 (MCP‐1) (p < 0.01) from 3T3‐L1 adipocytes, respectively, while ghrelin failed to enhance tumor necrosis factor‐α (TNF‐α), interleukin‐1β (IL‐1β), IL‐6, IL‐10 and adiponectin secretions. In addition, Akt phosphorylation on Ser473 and c‐Jun NH2‐terminal protein kinase (JNK) phosphorylation on Thr183/Tyr185 were markedly enhanced 1.4‐fold (p < 0.01) and 1.6‐fold (p < 0.01) in the ghrelin‐stimulated adipocytes, respectively. Furthermore, the treatment with LY294002 (50 μmol/L) and Wortmannin (10nmol/L), inhibitors of phosphatidylinositol 3‐kinase (PI3K), significantly decreased the amplified VEGF120 secretion by 29% (p < 0.01) and 28% (p < 0.01) relative to the cells stimulated by ghrelin alone, respectively, whereas these inhibitors had no effects on increased MCP‐1 release. On the other hand, JNK inhibitor SP600125 (10 μmol/L) clearly reduced the increased MCP‐1, but not VEGF120, release by 35% relative to the only ghrelin‐stimulated cells (p < 0.01).

In conclusion, ghrelin can enhance the secretions of proinflammatory adipokines, VEGF120 and MCP‐1, but fails to affect IL‐10 and adiponectin which are considered to be anti‐inflammatory adipokines. Moreover, this augmented VEGF120 release is invited through the activation of PI3K pathways and the MCP‐1 is through JNK pathways. Consequently, our results strongly suggest that ghrelin can induce the development of diabetes via its direct‐action in peripheral tissues as well as via in CNS. J. Cell. Physiol. 230: 199–209, 2015. © 2014 The Authors. Journal of Cellular Physiology Published by Wiley Periodicals, Inc.
Intrinsic Sex‐Linked Variations in Osteogenic and Adipogenic Differentiation Potential of Bone Marrow Multipotent Stromal Cells
Authors: Bragdon Beth , Burns Robert , Baker Amelia H. , Belkina Anna C. , Morgan Elise F. , Denis Gerald V. , Gerstenfeld Louis C. , Schlezinger Jennifer J.
Published: June 2014

Bone formation and aging are sexually dimorphic. Yet, definition of the intrinsic molecular differences between male and female multipotent mesenchymal stromal cells (MSCs) in bone is lacking. This study assessed sex‐linked differences in MSC differentiation in 3‐, 6‐, and 9‐month‐old C57BL/6J mice. Analysis of tibiae showed that female mice had lower bone volume fraction and higher adipocyte content in the bone marrow compared to age‐matched males. While both males and females lost bone mass in early aging, the rate of loss was higher in males. Similar expression of bone‐ and adipocyte‐related genes was seen in males and females at 3 and 9 months, while at 6 months, females exhibited a twofold greater expression of these genes. Under osteogenic culture conditions, bone marrow MSCs from female 3‐ and 6‐month‐old mice expressed similar levels of bone‐related genes, but significantly greater levels of adipocyte‐related genes, than male MSCs. Female MSCs also responded to rosiglitazone‐induced suppression of osteogenesis at a 5‐fold lower (10 nM) concentration than male MSCs. Female MSCs grown in estrogen‐stripped medium showed similar responses to rosiglitazone as MSCs grown in serum containing estrogen. MSCs from female mice that had undergone ovariectomy before sexual maturity also were sensitive to rosiglitazone‐induced effects on osteogenesis. These results suggest that female MSCs are more sensitive to modulation of differentiation by PPARγ and that these differences are intrinsic to the sex of the animal from which the MSCs came. These results also may explain the sensitivity of women to the deleterious effects of rosiglitazone on bone. J. Cell. Physiol. 230: 296–307, 2015. © 2014 Wiley Periodicals, Inc.
Discriminative functions and over‐training as class‐enhancing determinants of meaningful stimuli
Authors: Travis Robert W. , Fields Lanny , Arntzen Erik
Published: June 2014

Likelihood of equivalence class formation (yield) was influenced by pre‐class formation of simultaneous and successive discriminations, their mastery criteria, and overtraining of the successive discriminations. Each undergraduate in seven groups attempted to form two 3‐node, 5‐member equivalence classes (ABCDE). In the pictorial (PIC) group, meaningless nonsense syllables were used as the A, B, D, and E stimuli and meaningful pictures as the C stimuli. Nonsense syllables only were used in the other groups. The abstract (ABS) or 0‐0‐0 group involved no pre‐class training. In the 84‐0‐0, 84‐5‐0 and 84‐20‐0 groups, simultaneous discriminations were trained among C stimuli to a mastery criterion of 84 trials, followed by successive discriminations trained to mastery criteria of 0, 5, and 20 trials, respectively. In the 84‐20‐0, 84‐20‐100, and 84‐20‐500 groups, simultaneous and successive discriminations were trained as noted, followed by overtraining with 0, 100, 500 successive‐discrimination trials, respectively. The ABS group produced a 6% yield with the 84‐0‐0, 84‐5‐0, and 84‐20‐0 groups producing further modest increments. Overtraining produced a linear increase in yield, reaching 85% after 500 overtraining trials, a yield matching that produced by classes containing pictures as C stimuli (PIC). Thus, acquired discriminative functions and the overtraining of at least one function can account for class enhancement by meaningful stimuli.
Dim light at night interferes with the development of the short‐day phenotype and impairs cell‐mediated immunity in Siberian hamsters (Phodopus sungorus)
Authors: Aubrecht Taryn G. , Weil Zachary M. , Nelson Randy J.
Published: June 2014

Winter is a challenging time to survive and breed outside of the tropics. Animals use day length (photoperiod) to regulate seasonally appropriate adaptations in anticipation of challenging winter conditions. The net result of these photoperiod‐mediated adjustments is enhanced immune function and increased survival. Thus, the ability to discriminate day length information is critical for survival and reproduction in small animals. However, during the past century, urban and suburban development has rapidly expanded and filled the night sky with light from various sources, obscuring crucial light‐dark signals, which alters physiological interpretation of day lengths. Furthermore, reduced space, increased proximity to people, and the presence of light at night may act as stressors for small animals. Whereas acute stressors typically enhance immune responses, chronic exposure to stressors often impairs immune responses. Therefore, we hypothesized that the combination of dim light at night and chronic stress interferes with enhanced cell‐mediated immunity observed during short days. Siberian hamsters (Phodopus sungorus) were assigned to short or long days with dark nights (0 lux) or dim (5 lux) light at night for 10 weeks. Following 2 weeks of chronic restraint (6 hr/day), a model of chronic stress, delayed type hypersensitivity (DTH) responses were assessed. Both dim light at night and restraint reduced the DTH response. Dim light at night during long nights produced an intermediate short day phenotype. These results suggest the constant presence of light at night could negatively affect survival of photoperiodic rodents by disrupting the timing of breeding and immune responses. J. Exp. Zool. 321A: 450–456, 2014. © 2014 Wiley Periodicals, Inc.
Operant Psychology Makes a Splash—In Marine Mammal Training (1955–1965)
Authors: Gillaspy James Arthur , Brinegar Jennifer L. , Bailey Robert E.
Published: June 2014

Despite the wide spread use of operant conditioning within marine animal training, relatively little is known about this unique application of behavioral technology. This article explores the expansion of operant psychology to commercial marine animal training from 1955 to 1965, specifically at marine parks such as Marine Studios Florida, Marineland of the Pacific, Sea Life Park, and SeaWorld. The contributions of Keller and Marian Breland and their business Animal Behavior Enterprises (ABE) as well as other early practitioners of behavioral technology are reviewed. We also describe how operant technology was introduced and formalized into procedures that have become the cornerstone of marine animal training and entertainment. The rapid growth of the marine park industry during this time was closely linked to the spread of behavioral technology. The expansion of operant training methods within marine animal training is a unique success story of behavioral technology.
Unexpected Formation of 5‐Nitro‐1H‐benzimidazoles by Nucleophilic Recyclization of 1‐Methyl‐5‐nitropyridinium Salts
Authors: Sagitullina Galina P. , Garkushenko Anna K. , Novikov Alexey N. , Sagitullin Reva S.
Published: June 2014

The synthesis of substituted 5‐nitro‐2‐phenyl‐1H‐benzimidazoles has been described via domino anionic process rearrangement of 3‐benzoylamino‐1,2‐dimethyl‐5‐nitropyridinium salts in the presence of NaOH water–alcohol solution. Substituted N‐benzoyl‐o‐phenylenediamines was obtained via recyclization of 3‐benzoylamino‐1,2‐dimethyl‐5‐nitropyridinium salts in the presence of aqueous methylamine solution.
Steric and Electronic Requirements in the Synthesis of 2,3‐Dihydro‐4(1H)‐quinolinones by the Tandem Michael‐SNAr Reaction
Authors: Bunce Richard A. , Nago Takahiro , Abuskhuna Suaad
Published: June 2014

The steric and electronic requirements have been investigated for the synthesis of 2,3‐dihydro‐4(1H)‐quinolinones by the tandem Michael‐SNAr reaction. Substrates bearing a single methyl group at the β‐enone carbon gave excellent yields of the title compounds from both the E and Z isomers with X═H or NO2. Substrates with β,β‐dimethyl substitution at the Michael terminus gave low yields of heterocyclic products in molecules having monoactivated SNAr aromatic acceptor rings (X═H) and very good yields for diactivated systems (X═NO2). For these hindered substrates, success in the final cyclization hinges on the ability of the aromatic acceptor to capture the pendant nitrogen nucleophile of the initial Michael adduct before this intermediate can revert to starting materials.
One‐Pot Synthesis of 3‐Cyano‐2‐pyridones
Authors: Wang Yingcai , Liu Gang , Reyes Jeremy Chris P. , Duverna Randolph
Published: June 2014

A versatile synthesis of 3‐cyano‐2‐pyridones via a one‐pot, four‐component condensation of ethyl cyanoacetate, ketones, aldehydes, and ammonium acetate under very mild conditions has been developed. This method provides rapid access to this type of valuable heterocyclic compounds from readily available materials in a single operation.
Tetrakis‐(N‐pyrrolyl)methane: Structurally Important Member of the C(NR2)4 Family
Authors: Sun Guanxing , Butler Douglas N. , Warrener Ronald N. , Margetić Davor
Published: June 2014

The structural motif C(NR2)4 is rare in chemistry. The formation, NMR spectroscopic characteristics, and X‐ray structure are reported for a structurally interesting member of this family, namely tetrakis‐(N‐pyrrolyl)methane.
A Facile Synthesis of Oxoindenothiazine and Dioxospiro(indene‐2,4′‐thiazine) Derivatives from (Substituted ethylidene)hydrazinecarbothioamides
Authors: Hassan Alaa A. , Ibrahim Yusria R. , El‐Sheref Essmat M. , Ibrahim Mahmoud A. A. , Bräse Stefan
Published: June 2014

(E)‐2‐[2‐(1‐Substituted ethylidene)hydrazinyl]‐5‐oxo‐9b‐hydroxy‐5,9b‐dihydroindeno[1,2‐d][1,3]‐thiazine‐4‐carbonitriles and (E)‐5‐oxo‐[(E)‐(1‐substituted ethylidene)hydrazinyl]‐2,5‐dihydroindeno[1,2‐d][1,3]thiazine‐4‐carbonitriles have been obtained from the reaction of 2‐(substituted ethylidene)hydrazinecarbothioamides with 2‐(1,3‐dioxo‐2,3‐dihydro‐1H‐inden‐2‐ylidene)propanedinitrile (1) in ethyl acetate solution. However, (Z)‐6′‐amino‐1,3‐dioxo‐3′‐substituted‐2′‐[(E)‐(1‐phenylethylidene)hydrazono]‐1,2′,3,3′‐tetrahydrospiro(indene‐2,4′‐[1,3]thiazine)‐5′‐carbonitriles were observed during the reaction of N‐substituted‐2‐(1‐phenylethylidene)hydrazinecarbothioamides with (1). The structure assignment of products has been confirmed on the basis of 1H‐, 13C‐NMR, and mass spectrometry, as well as theoretical calculations.
Design, Synthesis, and Biological Evaluations of Several Y‐26732 Analogues
Authors: Wang Xinran , Chen Ligong , Li Hang , Sun Changhai , Qi Haofei , Wang Donghua
Published: June 2014

A series of pyridine Rho kinase inhibitors were designed and synthesized utilizing the ligand‐binding pocket model with Y‐26732 as the lead compound. These compounds were evaluated on cell lines for their biological activities.
Effects of acute ozone stress on reproductive traits of tomato, fruit yield and fruit composition
Authors: Thwe Aye Aye , Vercambre Gilles , Gautier Hélène , Gay Frédéric , Phattaralerphong Jessada , Kasemsap Poonpipope
Published: June 2014

BACKGROUND

Tomato is sensitive to ozone. Fruit growth and composition are altered under ozone stress by modification of reproductive development. Fifty‐one‐day‐old plants were exposed to three concentrations of ozone (200, 350 and 500 µg m−3) for 4 h.

RESULTS

Ozone reduced well‐developed fruit number and fruit size, but it did not significantly affect flowering rate and fruit setting rate. The effect of ozone depends on organ developmental stage at the time of ozone application, as flowers and young fruits at the time of ozone exposure were more affected. Contents of total soluble sugars (total SS), total organic acids (total OA) and ascorbic acid (AsA) increased in fruits harvested from ozone‐treated plants. Tomato fruit composition was altered under ozone stress, leading to a lower sugar:acid ratio. These changes were mostly due to increased contents of malic acid, ascorbate and glucose despite a decrease in sucrose.

CONCLUSION

Acute ozone exposure up to 500 µg m−3 greatly influences tomato fruit quality. As final fruit yield was not significantly reduced, it highlighted that there may be compensatory mechanisms present in the reproductive structures of tomato. Further research would be necessary to determine how reproductive traits are affected by repeated ozone exposure or longer‐term exposure. © 2014 Society of Chemical Industry