bluuebunny/crossref_metadata_2025 huggingface dataset:
Nonsteroidal anti‐inflammatory drugs–exacerbated respiratory disease in adolescents
Authors: Ertoy Karagol Hacer Ilbilge , Yilmaz Ozlem , Topal Erdem , Ceylan Alper , Bakirtas Arzu
Published: March 2015

Background

There has been no study investigating nonsteroidal anti‐inflammatory drugs (NSAIDs)‐exacerbated respiratory disease (NERD) exclusively in childhood. Therefore, in the current study, the authors aimed to evaluate the diagnostic features, clinical characteristics, and follow‐up of adolescents diagnosed with NERD.

Methods

The patients who were consecutively diagnosed with NERD between January 2011, and November 2013, included in the study. Oral provocation test (OPT) with at least 2 different NSAIDs was used to confirm NSAID hypersensitivity in patients with underlying asthma/chronic rhinosinusitis/nasal polyps. All patients were followed regularly in 3‐month intervals by the Pediatric Allergy and Otorhinolaryngology Department for asthma, allergic rhinitis, or chronic rhinosinusitis with or without nasal polyps.

Results

A total of 10 adolescents with NERD were included in the study. The mean age of the patients at the time of diagnosis was 14.9 ± 1.5 years. Hives or angioedema accompanied respiratory complaints induced by NSAIDs. The mean duration of follow‐up was 28.9 ± 12.4 months. All patients had asthma except 1 with asymptomatic bronchial hyperreactivity. Asthma of patients was well‐controlled with moderate dose of inhaled corticosteroids. Chronic rhinosinusitis with or without nasal polyps developed in 2 patients. Aspirin desensitization was required in these 2 patients with recurrent nasal polyps.

Conclusion

NERD in childhood has much more favorable clinical characteristics and course than in adulthood. Few adolescents with NERD refer with typical chronic upper respiratory tract complaints. The asthma component seems to be mild and is well controlled in the short‐term follow‐up.
Influence of upper airway abnormalities on the control of severe asthma: a cross‐sectional study
Authors: Soares Nascimento‐Sampaio Francisco , dos Santos Leite Mylene , Leopold Donald Arthur , Guedes Oliva da Silva Suzam , Schwingel Paulo Adriano , Cardeal Mendes Carlos Maurício , Souza‐Machado Adelmir , de Albuquerque Campos Régis
Published: March 2015

Background

A better understanding of severe uncontrolled asthma (UA) in the upper airways is needed. The aims of this study were to assess the prevalence of upper airway abnormalities and their associations with UA.

Methods

An observational study enrolled individuals with severe asthma. Sociodemographic and clinical questionnaires regarding asthma, rhinosinusitis, and laryngopharyngeal reflux (LPR) were administered. Skin‐prick tests and fiber optic nasolaryngoscopies were also performed. Descriptive statistical analysis was performed, using a multiple Poisson regression model to obtain adjusted prevalence ratios (PRs) and to identify the clinical profiles associated with the highest and lowest percentages of the dependent variable, lack of asthma control.

Results

The sample consisted of 64 participants who were divided into 2 groups according to asthma control. Thus, group I comprised 27 individuals with severe controlled asthma (CA), and group II consisted of 37 individuals with UA. Women represented 87.5% of the study population. The median age was 54 years, and 86% of the sample had rhinosinusitis. Relevant associations were detected between UA and hyposmia (PR = 2.04), hypersensitivity to nonsteroidal anti‐inflammatory drugs (NSAIDs) (PR = 1.45), arytenoids hyperemia (PR = 1.45), LPR (PR = 1.37), a positive family history of asthma (PR = 1.35), onset of asthma at age 10 years or older (PR = 0.59), and swelling of the vocal cords (PR = 0.54).

Conclusion

This study found a very high prevalence of rhinosinusitis in patients with severe asthma as well as associations between UA and hyposmia, hypersensitivity to NSAIDs, arytenoids hyperemia, and LPR. Clinical profiles prone to UA were identified.
Interleukin‐17A–induced inflammation does not influence the development of nasal polyps in murine model
Authors: Hong Sung‐Lyong , Zhang Yu‐Lian , Kim Sang‐Wook , Kim Dae Woo , Cho Sang‐Heon , Chang Yoon‐Seok , Lee Chul Hee , Rhee Chae‐Seo
Published: March 2015

Background

Nasal polyposis associated with chronic rhinosinusitis (CRS) is a chronic inflammatory disease that is characterized by infiltration of many inflammatory cells. Meanwhile, interleukin (IL)‐17A is a well‐known proinflammatory cytokine that induces both eosinophilic and neutrophilic inflammation. We investigated the role of IL‐17A in the development of nasal polyps in the CRS murine model.

Methods

Eosinophilic CRS with nasal polyps was induced by using ovalbumin (OVA) and Staphylococcus aureus enterotoxin B (SEB) in wild‐type BALB/c and IL‐17A knockout (KO) mice. Histopathologic changes of the sinonasal cavity were evaluated using hematoxylin and eosin, Periodic acid‐Schiff, Sirius red, Masson's trichrome, and immunohistochemistry. The levels of total and OVA‐specific immunoglobulin Es (IgEs) in sera were measured using enzyme‐linked immunosorbent assay. The expression levels of IL‐4, IL‐5, and interferon‐γ (IFN‐γ) in the nasal mucosa were assessed by quantitative real‐time polymerase chain reaction.

Results

Under the IL‐17A deficiency, total and OVA‐specific IgEs in sera were reduced significantly. Infiltration of both eosinophils and neutrophils into the nasal mucosa, subepithelial fibrosis, and goblet cell count also decreased significantly in IL‐17A KO mice treated with both OVA and SEB compared with those in the wild‐type counterpart. However, there were no significant differences in the number of polypoid lesions among groups. Meanwhile, IL‐4 increased and IFN‐γ decreased in the nasal mucosa in IL‐17A KO mice treated with both OVA and SEB.

Conclusion

This study suggests that even though IL‐17A plays an important role in both nasal inflammation and remodeling, it does not influence the development of nasal polypoid lesions.
Prediction model for 3‐year rupture risk of unruptured cerebral aneurysms in Japanese patients
Authors: Tominari Shinjiro , Morita Akio , Ishibashi Toshihiro , Yamazaki Tomosato , Takao Hiroyuki , Murayama Yuichi , Sonobe Makoto , Yonekura Masahiro , Saito Nobuhito , Shiokawa Yoshiaki , Date Isao , Tominaga Teiji , Nozaki Kazuhiko , Houkin Kiyohiro , Miyamoto Susumu , Kirino Takaaki , Hashi Kazuo , Nakayama Takeo ,   for the Unruptured Cerebral Aneurysm Study Japan Investigators
Published: March 2015

Objective

To build a prediction model that estimates the 3‐year rupture risk of unruptured saccular cerebral aneurysms.

Methods

Survival analysis was done using each aneurysm as the unit for analysis. Derivation data were from the Unruptured Cerebral Aneurysm Study (UCAS) in Japan. It consists of patients with unruptured cerebral aneurysms enrolled between 2000 and 2004 at neurosurgical departments at tertiary care hospitals in Japan. The model was presented as a scoring system, and aneurysms were classified into 4 risk grades by predicted 3‐year rupture risk: I, < 1%; II, 1 to 3%; III, 3 to 9%, and IV, >9%. The discrimination property and calibration plot of the model were evaluated with external validation data. They were a combination of 3 Japanese cohort studies: UCAS II, the Small Unruptured Intracranial Aneurysm Verification study, and the study at Jikei University School of Medicine.

Results

The derivation data include 6,606 unruptured cerebral aneurysms in 5,651 patients. During the 11,482 aneurysm‐year follow‐up period, 107 ruptures were observed. The predictors chosen for the scoring system were patient age, sex, and hypertension, along with aneurysm size, location, and the presence of a daughter sac. The 3‐year risk of rupture ranged from <1% to >15% depending on the individual characteristics of patients and aneurysms. External validation indicated good discrimination and calibration properties.

Interpretation

A simple scoring system that only needs easily available patient and aneurysmal information was constructed. This can be used in clinical decision making regarding management of unruptured cerebral aneurysms. Ann Neurol 2015;77:1050–1059
Positron annihilation and other experimental studies on polycarbonate/MPDMAPP nanocomposite
Authors: Thimmaiah Sheela , Bhajantri Rajashekhar Fakeerappa , Nambissan Padinharu Madathil Gopalakrishnan , Vasachar Ravindrachary , Rathod Sunil Gurunath , Poojary Boja
Published: March 2015

The composite films of polycarbonate (PC) filled with 1‐(4‐methylphenyl)‐3‐(4‐N,N‐dimethylaminophenyl)‐2‐propen‐1‐one (MPDMAPP) were prepared by solution casting. The FT‐IR results of the prepared films confirmed the hydrophobic and dipole‐dipole interaction between PC and MPDMAPP, which is a major driving force for the formation of charge transfer complex (CTC). UV–Vis absorption spectra showed three peaks and the optical band gap Eg for pure PC is 4.31 eV which decreased to 4.1 eV after 15 wt % doping. The fluorescence spectral results show a strong emission and quenching in the wavelength region 510 to 550 nm for 408 nm excitation due to increase in amorphousness, which is observed in X‐ray diffraction (XRD) results. The decrease in ortho‐positronium (o‐Ps) lifetime τ3 and corresponding intensity I3 from positron annihilation lifetime spectroscopy (PALS) and the S‐parameter from Doppler broadening measurements show both inhibition and quenching of Ps formation in the PC/MPDMAPP composite due to the presence of dimethylamino N(CH3)2 group. The mechanical properties such as Young's modulus, tensile strength, and stiffness increase with doping concentration and confirmed that the composite films are mechanically stable. The growth of nanostructures of MPDMAPP within PC films is studied with SEM and TEM images and confirms the uniform dispersion and interaction between the functional groups of PC and MPDMAPP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42053.
Modification of daunorubicin‐GnRH‐III bioconjugates with oligoethylene glycol derivatives to improve solubility and bioavailability for targeted cancer chemotherapy
Authors: Hegedüs Rózsa , Pauschert Aline , Orbán Erika , Szabó Ildikó , Andreu David , Marquardt Andreas , Mező Gábor , Manea Marilena
Published: March 2015

Daunorubicin‐GnRH‐III bioconjugates have recently been developed as drug delivery systems with potential applications in targeted cancer chemotherapy. In order to improve their biochemical properties, several strategies have been pursued: (1) incorporation of an enzymatic cleavable spacer between the anticancer drug and the peptide‐based targeting moiety, (2) peptide modification by short chain fatty acids, or (3) attachment of two anticancer drugs to the same GnRH‐III derivative. Although these modifications led to more potent bioconjugates, a decrease in their solubility was observed. Here we report on the design, synthesis and biochemical characterization of daunorubicin‐GnRH‐III bioconjugates with increased solubility, which could be achieved by incorporating oligoethylene glycol‐based spacers in their structure. First, we have evaluated the effect of an oligoethylene glycol‐based spacer on the solubility, enzymatic stability/degradation, cellular uptake, and in vitro cytostatic effect of a bioconjugate containing only one daunorubicin attached through a GFLG tetrapeptide spacer to the GnRH‐III targeting moiety. Thereafter, more complex compounds containing two copies of daunorubicin, GFLG spacers as well as Lys(nBu) in position 4 of GnRH‐III were synthesized and biochemically characterized. Our results indicated that all synthesized oligoethylene glycol‐containing bioconjugates had higher solubility in cell culture medium than the unmodified analogs. They were degraded in the presence of rat liver lysosomal homogenate leading to the formation of small drug containing metabolites. In the case of bioconjugates containing two copies of daunorubicin, the incorporation of oligoethylene glycol‐based spacers led to increased in vitro cytostatic effect on MCF‐7 human breast cancer cells. © 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 104: 167–177, 2015.
Mental illness and parenthood: being a parent in secure psychiatric care
Authors: Parrott Fiona R. , Macinnes Douglas l. , Parrott Janet
Published: March 2015

Background

Research into parenting and mental illness seldom includes forensic mental health service users, despite its relevance to therapeutic, family work and risk management.

Aims

This study aimed to understand the experiences of parents and the variety of parenting roles maintained during admission to a secure forensic hospital.

Methods

Narrative interviews with 18 parents (eight mothers and 10 fathers) at an English medium security hospital were analysed thematically, using the framework approach. The proportion of patients who are parents and their contact patterns with their children were estimated from records.

Results

About a quarter of men and 38% of women were parents. Parenthood was of central importance to their emotional life, spanning experiences of loss, shame and failed expectations, joy, responsibility and hope. Fewer fathers maintained contact with their children than mothers yet fatherhood remained a vital aspect of men's identities, with impact on their self‐esteem. Parenting during lengthy admissions – while constrained and dependent on professional support and surveillance – ranged from sending gifts and money to visits and phone calls. Offending was seen as a particularly shameful aspect of admission, contributing to distancing from the children and difficulty explaining detention to them.

Conclusions

Such complex experiences call for multidisciplinary knowledge and skills. Provision of focused therapy, as well as appropriate visiting spaces, creative approaches to contact time and support for patients in explaining their mental illness and detention to their children are recommended. © 2015 The Authors. Criminal Behaviour and Mental Health published by John Wiley & Sons Ltd.
Application of a Semi‐Mechanistic Model for Cracking Unit Balance
Authors: Karaba Adam , Zamostny Petr , Belohlav Zdenek , Lederer Jaromir , Herink Tomas
Published: March 2015

A kinetic model of steam‐cracking in industrial‐scale steam crackers was developed by a combination of mechanistic and empirical approach. Kinetic parameters of the model were optimized using the data of process experiments, carried out in full‐scale industrial crackers, the product yields being determined by hot‐gas sampling for the usual types of feedstock, including ethane, liquefied petroleum gas, gasoline, atmospheric gas oil, and hydrocracked vacuum distillate. Experimental and simulated results were compared for a wide range of feedstock and reaction conditions. Data on cracker control parameters and feedstock composition were collected by monitoring the whole production unit consisting of ten crackers and simulation results of total production compared to those of process balance.
Flashpoint Prediction for Binary Mixtures of Alcohols with Water in Order to Improve their Safety
Authors: Skřínský Jan , Dolníček Petr , Skřínská Maria , Marek Jan , Lukešová Petra
Published: March 2015

Aqueous solutions of alcohols are of considerable interest for a wide range of scientists and technologists. Simple dimensionless experimental formulae based on rational reciprocal and polynomial functions are proposed for correlation of the flashpoint data of binary mixtures of two components. The formulae are based on data obtained from flashpoint experiments and predictions. The main results are the derived flashpoint approximated values and the model verification by comparing the predicted values with the experimental data for the studied mixtures. Potential application for the model concerns the assessment of fire and explosion hazards, and the development of inherently safer designs for chemical processes containing binary partially miscible mixtures of an aqueous‐organic system.
One‐Pot Synthesis of Platinum–Ceria/Graphene Nanosheet as Advanced Electrocatalysts for Alcohol Oxidation
Authors: Zhang Ling , Shen Yi
Published: March 2015

A three‐component platinum–ceria/graphene nanosheet hybrid (Pt–CeO2−x/GNS) was prepared through a facile one‐pot synthesis method and examined as an electrocatalysts for alcohol (methanol, ethanol, ethylene glycol, and glycerol) oxidation. The structures of the catalysts were characterized by using transmission electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy (XPS). It was found that ultrafine Pt particles were intimately deposited at the interface of the CeO2−x and GNS support, resulting in the formation of abundant Pt–CeO2−x/GNS triple junctions in the hybrid. XPS results indicated a strong metal–support interaction in the catalyst. It was demonstrated that Pt–CeO2−x/GNS showed superior catalytic performance in comparison with the Pt/GNS catalyst. The superior catalytic performance of the Pt–CeO2−x/GNS catalyst was attributed to the presence of Pt–CeO2−x/GNS triple junctions, which facilitated the synergistic effects of the constituents.
Non‐enzymatic Ribonucleotide Reduction in the Prebiotic Context
Authors: Dragičević Ivan , Barić Danijela , Kovačević Borislav , Golding Bernard T. , Smith David M.
Published: March 2015

Model studies of prebiotic chemistry have revealed compelling routes for the formation of the building blocks of proteins and RNA, but not DNA. Today, deoxynucleotides required for the construction of DNA are produced by reduction of nucleotides catalysed by ribonucleotide reductases, which are radical enzymes. This study considers potential non‐enzymatic routes via intermediate radicals for the ancient formation of deoxynucleotides. In this context, several mechanisms for ribonucleotide reduction, in a putative H2S/HS. environment, are characterized using computational chemistry. A bio‐inspired mechanistic cycle involving a keto intermediate and HSSH production is found to be potentially viable. An alternative pathway, proceeding through an enol intermediate is found to exhibit similar energetic requirements. Non‐cyclical pathways, in which HSS. is generated in the final step instead of HS., show a markedly increased thermodynamic driving force (ca. 70 kJ mol−1) and thus warrant serious consideration in the context of the prebiotic ribonucleotide reduction.
Single‐Atom Gold Catalysis in the Context of Developments in Parahydrogen‐Induced Polarization
Authors: Corma Avelino , Salnikov Oleg G. , Barskiy Danila A. , Kovtunov Kirill V. , Koptyug Igor V.
Published: March 2015

A highly isolated monoatomic gold catalyst, with single gold atoms dispersed on multiwalled carbon nanotubes (MWCNTs), has been synthesized, characterized, and tested in heterogeneous hydrogenation of 1,3‐butadiene and 1‐butyne with parahydrogen to maximize the polarization level and the contribution of the pairwise hydrogen addition route. The Au/MWCNTs catalyst was found to be active and efficient in pairwise hydrogen addition and the estimated contributions from the pairwise hydrogen addition route are at least an order of magnitude higher than those for supported metal nanoparticle catalysts. Therefore, the use of the highly isolated monoatomic catalysts is very promising for production of hyperpolarized fluids that can be used for the significant enhancement of NMR signals. A mechanism of 1,3‐butadiene hydrogenation with parahydrogen over the highly isolated monoatomic Au/MWCNTs catalyst is also proposed.
Pd‐Catalyzed Difluoromethylation of Vinyl Bromides, Triflates, Tosylates, and Nonaflates
Authors: Chang Dalu , Gu Yang , Shen Qilong
Published: March 2015

Pd‐catalyzed difluoromethylation of di‐, tri‐ or tetra‐substituted vinyl bromides, triflates, tosylates and nonaflates under mild conditions is described. The reaction tolerates a wide range of functional groups, such as bromide, chloride, fluoride, ester, amine, nitrile, and protected carbonyl, thus providing a general route for the preparation of difluoromethylated alkenes.
Die Modellierung von Stofftransportprozessen in Mehrphasenströmungen – am Beispiel des Strahlzonen‐Schlaufenreaktors
Authors: Heithoff Susanne , Kück Ulf Daniel , Mießner Ulrich , Schlüter Michael
Published: March 2015

Umsatz und Selektivität chemischer Reaktionen werden durch die Vermischungscharakteristik im Reaktionsraum bestimmt. In vielen Modellen wird diese vereinfacht integral gemittelt betrachtet. Durch die Vernachlässigung der vorherrschenden örtlichen Transportphänomene ist die Auslegung von Anlagen insbesondere bei stofftransportlimitierten Reaktionen nicht optimal. In Mehrphasensystemen müssen im Wesentlichen zwei Transportprozesse Beachtung finden: Diffusion durch die sich zwischen Gas‐ und Flüssigphase einstellende Konzentrationsgrenzschicht und innerhalb der Batchelorschicht. Im Beitrag werden die auf den Stofftransport wirkenden Mechanismen dargestellt. Erste Untersuchungsergebnisse von lokalen Stofftransportprozessen im mit Zweiphasenströmung betriebenen Strahlzonen‐Schlaufenreaktor werden diskutiert.
β‐Functionalized Push–Pull Porphyrin Sensitizers in Dye‐Sensitized Solar Cells: Effect of π‐Conjugated Spacers
Authors: Ishida Masatoshi , Hwang Daesub , Zhang Zhan , Choi Yung Ji , Oh Juwon , Lynch Vincent M. , Kim Dong Young , Sessler Jonanthan L. , Kim Dongho
Published: March 2015

A series of new β‐functionalized push–pull‐structured porphyrin dyes were synthesized so as to investigate the effect of the π‐conjugated spacer on the performance of dye‐sensitized solar cells (DSSCs). Suzuki‐ and Heck‐type palladium‐catalyzed coupling methodologies were used to obtain various β‐functionalized porphyrins and β‐benzoic acid (ZnPHn) and β‐vinylbenzoic acid (ZnPVn) derivatives from β‐borylated porphyrin precursors. Photophysical studies of the resulting porphyrins revealed a clear dependence on the nature of the β linker. In particular, it was found that a β‐vinylene linkage perturbs the electronic structure of the porphyrin core; this is less true for a β‐phenyl linkage. Theoretical analyses provided support for the intrinsic intramolecular charge‐transfer character of the β‐functionalized, push–pull porphyrins of this study. The extent of charge transfer depends on the nature of the β‐conjugated linkage. The photovoltaic performances of the cells sensitized with β‐phenylenevinylene ZnPVn exhibited higher power conversion efficiency values than those bearing β‐phenyl linkages (ZnPHn). This was ascribed to differences in light‐harvesting efficiency. Furthermore, compared to the use of a standard iodine‐based electrolyte, the DSSC performance of cells made from the present porphyrins was improved by more than 1 % upon using a cobalt(II/III)‐based electrolyte. Under standard AM 1.5 illumination, the highest efficiency, 8.2 %, was obtained by using cells made from the doubly β‐butadiene‐linked porphyrin.
Does natural selection explain the fine scale genetic structure at the nuclear exon Glu‐5′ in blue mussels from Kerguelen?
Authors: Gérard Karin , Roby Charlotte , Bierne Nicolas , Borsa Philippe , Féral Jean‐Pierre , Chenuil Anne
Published: March 2015

The Kerguelen archipelago, isolated in the Southern Ocean, shelters a blue mussel Mytilus metapopulation far from any influence of continental populations or any known hybrid zone. The finely carved coast leads to a highly heterogeneous habitat. We investigated the impact of the environment on the genetic structure in those Kerguelen blue mussels by relating allele frequencies to habitat descriptors. A total sample comprising up to 2248 individuals from 35 locations was characterized using two nuclear markers, mac‐1 and Glu‐5′, and a mitochondrial marker (COI). The frequency data from 9 allozyme loci in 9 of these locations were also reanalyzed. Two other nuclear markers (EFbis and EFprem's) were monomorphic. Compared to Northern Hemisphere populations, polymorphism in Kerguelen blue mussels was lower for all markers except for the exon Glu‐5′. At Glu‐5′, genetic differences were observed between samples from distinct regions (FCT = 0.077), as well as within two regions, including between samples separated by <500 m. No significant differentiation was observed in the AMOVA analyses at the two other markers (mac‐1 and COI). Like mac‐1, all allozyme loci genotyped in a previous publication, displayed lower differentiation (Jost's D) and FST values than Glu‐5′. Power simulations and confidence intervals support that Glu‐5′ displays significantly higher differentiation than the other loci (except a single allozyme for which confidence intervals overlap). AMOVA analyses revealed significant effects of the giant kelp Macrocystis and wave exposure on this marker. We discuss the influence of hydrological conditions on the genetic differentiation among regions. In marine organisms with high fecundity and high dispersal potential, gene flow tends to erase differentiation, but this study showed significant differentiation at very small distance. This may be explained by the particular hydrology and the carved coastline of the Kerguelen archipelago, together with spatially variable selection at Glu‐5′.
Nutrient levels within leaves, stems, and roots of the xeric species Reaumuria soongorica in relation to geographical, climatic, and soil conditions
Authors: He Mingzhu , Zhang Ke , Tan Huijuan , Hu Rui , Su Jieqiong , Wang Jin , Huang Lei , Zhang Yafeng , Li Xinrong
Published: March 2015

Besides water relations, nutrient allocation, and stoichiometric traits are fundamental feature of shrubs. Knowledge concerning the nutrient stoichiometry of xerophytes is essential to predicting the biogeochemical cycling in desert ecosystems as well as to understanding the homoeostasis and variability of nutrient traits in desert plants. Here, we focused on the temperate desert species Reaumuria soongorica and collected samples from plant organs and soil over 28 different locations that covered a wide distributional gradient of this species. Carbon (C), nitrogen (N), and phosphorus (P) concentrations and their stoichiometry were determined and subsequently compared with geographic, climatic, and edaphic factors. The mean leaf C, N, and P concentrations and C/N, C/P, and N/P ratios were 371.6 mg g−1, 10.6 mg g−1, 0.73 mg g−1, and 59.7, 837.9, 15.7, respectively. Stem and root C concentrations were higher than leaf C, while leaf N was higher than stem and root N. Phosphorus concentration and N/P did not differ among plant organs. Significant differences were found between root C/N and leaf C/N as well as between root C/P and leaf C/P. Leaf nutrient traits respond to geographic and climatic factors, while nutrient concentrations of stems and roots are mostly affected by soil P and pH. We show that stoichiometric patterns in different plant organs had different responses to environmental variables. Studies of species‐specific nutrient stoichiometry can help clarify plant–environment relationships and nutrient cycling patterns in desert ecosystems.
Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties
Authors: Recatalá David , Llusar Rosa , Galindo Francisco , Brylev Konstantin A. , Gushchin Artem L.
Published: March 2015

Neutral Mo3(μ3‐S)(μ‐S2)3X3(diimine) (X = Cl–, Br–) heteroleptic cluster complexes containing the 1,10‐phenanthroline ligands 1H‐imidazo[4,5‐f][1,10]phenanthroline‐2‐[3,4‐bis(dodecyloxy)phenyl] (IPDOP), 4,7‐diphenyl‐1,10‐phenanthroline (BPhen), and 3,4,7,8‐tetramethyl‐1,10‐phenanthroline (tmphen) were prepared in high yields by straightforward ligand‐substitution reactions starting from the [Mo3(μ3‐S)(μ‐S2)3X6]2– cluster anion. The complexes Mo3S7X4(BPhen) [X = Br– (for 3) and Cl– (for 4)] and Mo3S7X4(tmpphen) [X = Br– (for 5) and Cl– (for 6)] crystallized as tetra‐n‐butylammonium salts of anionic aggregates (3–6·X)–, in which neutral Mo3S7X3(diiimine)3 cluster molecules participate in non‐valence interactions between the axial sulfur atoms, Sax, and a halide anion. The complexes Mo3S7Br4(IPDOP) (1) and Mo3S7Cl4(IPDOP) (2) are luminescent when excited at 330 nm and have maximum emission intensities around 450 nm in DMF and around 435 nm in dichloromethane. The maximum fluorescence quantum yield and the maximum emission lifetime were achieved for complex 2 in DMF(φF = 0.15 and τ = 7.5 ns, respectively). The most important property of complexes 1 and 2 is the shift of their emission spectra in the presence of proton‐abstractor anions, such as F–, OH–, and AcO–. When these anions are added to solutions of complexes 1 or 2 in DMF or dichloromethane, the maximum emission wavelength shifts by approximately 90 nm to higher wavelengths.
PEPPSI‐Effect on Suzuki–Miyaura Reactions Using 4,5‐Dicyano‐1,3‐dimesitylimidazol‐2‐ylidene‐Palladium Complexes: A Comparison between trans‐Ligands
Authors: Baier Heiko , Kelling Alexandra , Holdt Hans‐Jürgen
Published: March 2015

The PEPPSI (Pyridine Enhanced Precatalyst Preparation, Stabilization and Initiation) complexes 12–15 with the structure [PdCl2{(CN)2IMes}(3‐R‐py)] (12: R = H; 13: R = Cl; 14: R = Br; 15: R = CN) bearing the maleonitrile‐based N‐heterocyclic carbene (NHC) (CN)2IMes ({(CN)2IMes}: 4,5‐dicyano‐1,3‐dimesitylimidazol‐2‐ylidene) were prepared. Solid state structures of 14 and 15 were obtained. Complexes 14 and 15 adopt a slightly distorted square‐planar coordination geometry in the solid state with the substituted pyridine ligand trans to the NHC. Catalytic activities of precatalysts 12–15 were studied and subsequently compared to complexes [PdCl2{(CN)2IMes}(PPh3)] (4) and [PdCl(dmba){(CN)2IMes}] (5) recently reported by our group in the Suzuki–Miyaura reaction of various aryl halides and phenylboronic acid. Reactions using previously reported [PdCl2(IMes)(py)] (IMes: 1,3‐dimesitylimidazol‐2‐ylidene) (1) were also carried out and their results contrasted to those involving 12–15, 4 and 5. Differences in initiation rates and the catalytically active species related to the seven complexes in regards to the “throw away ligand” were investigated. Poisoning experiments with mercury show that palladium nanoparticles are responsible for the catalytic activity.
Chiral Radical‐Cation Salts of BEDT‐TTF Containing a Single Enantiomer of Tris(oxalato)aluminate(III) and ‐chromate(III)
Authors: Martin Lee , Akutsu Hiroki , Horton Peter N. , Hursthouse Michael B. , Harrington Ross W. , Clegg William
Published: March 2015

Radical‐cation salts of BEDT‐TTF with chiral anions provide the opportunity to combine chirality with conductivity in the same molecular material. We report here two salts, (BEDT‐TTF)3NaAl(C2O4)3·nitromethane and (BEDT‐TTF)3(NH4)0.83Cr1.17(C2O4)3·nitromethane. The former crystallises in space group P21 and the latter in P212121. The use of nitromethane alone as the electrolyte for electrocrystallisation produces no crystals, but the addition of chiral (R)‐(–)‐carvone yields crystals of these two new chiral radical‐cation salts of BEDT‐TTF through chiral induction from racemic tris(oxalato)aluminate(III) and tris(oxalato)chromate starting materials. The honeycomb anion layers in these salts contain a single enantiomer of tris(oxalato)metallate and creates hexagonal cavities that are smaller than those found in the superconducting β″ salts in this tris(oxalate)metallate family, which gives preference for smaller solvents to be included, such as nitromethane. The chromium salt has a non‐stoichiometric composition of the anion layer, which provides an electron doping effect to the donor layer.
Samarium Diiodide Mediated Coupling of 2‐Pyridylsulfonyl Furanosides with Aldehydes and Ketones: A General Synthesis of C‐Furanosides
Authors: Wang Jin , Gasc Fabien , Prandi Jacques
Published: March 2015

Diiodosamarium‐mediated coupling of anomeric 2‐pyridyl sulfones derived from furanosides with carbonyl compounds, aldehydes, and ketones gave α‐hydroxylated 2,5‐trans‐dialkylated tetrahydrofurans with good yields and useful stereoselectivities. The main control element of the reaction is the substituent on the 4‐position or the starting furanosyl sulfone. C‐Furanosides of D‐arabinose and of D‐ribose were obtained from sulfones prepared from the corresponding furanosides. Finally, a di‐C‐arabinofuranoside, a C‐disaccharide analogue of a major motif of the arabinogalactan from the mycobacterial cell wall, was prepared.
Reactions of Alkynyl‐ and 1,1′‐Dialkynylferrocenes with Tetracyanoethylene – Unanticipated Addition at the Less Electron‐Rich of Two Triple Bonds
Authors: Krauße Nico , Kielmann Marc , Ma Jingxiang , Butenschön Holger
Published: March 2015

Alkynylferrocenes react with tetracyanoethylene (TCNE) to form 2‐ferrocenyl‐1,1,4,4‐tetracyanobutadienes. These reactions occur under mild reaction conditions in almost quantitative yields if the triple bond is electron‐rich. Systems with more than one triple bond, namely, 1,1′‐dialkynylferrocenes or diynylferrocenes, react once at the more electron‐rich triple bond, and the second reaction cannot be achieved, even under more‐forcing reaction conditions. For a diyne with the reactivity switched by oxidation of the ferrocenyl moiety to the corresponding ferrocenium salt, the addition of TCNE occurred at the less electron‐rich triple bond. This unprecedented reactivity is explained by the resonance stabilization of a diradical intermediate. A push–pull 1,1′‐dialkynylferrocene with a [4‐(dimethylamino)phenyl]ethynyl and a (4‐nitrophenyl)ethynyl substituent reacted exclusively at the [4‐(dimethylamino)phenyl]ethynyl triple bond.
Palladium‐Catalyzed Amination of Aryl Sulfides with Aliphatic Amines
Authors: Gao Ke , Yorimitsu Hideki , Osuka Atsuhiro
Published: March 2015

Conditions for the palladium–NHC‐catalyzed amination of aryl sulfides with aliphatic as well as aromatic amines were established. The KHMDS‐mediated amination of heteroaryl sulfides could proceed without palladium. Based on the distinct difference in reactivity of C–Br and C–S bonds, a sequential amination of bromothioanisole can take place to install two different alkylamino groups onto the aromatic ring in one pot.
HIV‐related stigma in social interactions: Approach and avoidance behaviour in a virtual environment
Authors: Toppenberg Henna L. , Bos Arjan E. R. , Ruiter Robert A. C. , Wigboldus Daniël H. J. , Pryor John B.
Published: March 2015

People living with HIV are a stigmatized group in our society, especially homosexual people living with HIV. One of the behavioural manifestations of stigmatization is an increased interpersonal distance kept during social interactions. Immersive virtual environment technology enables the experimental study of social interactions in an accurate and relatively unobtrusive manner. Using a virtual hospital room, we measured to what extent diagnosis (HIV, cancer or broken leg) and sexual orientation (homosexual or heterosexual) were related to approach behaviour (based on the interpersonal distance and the speed of approach), and the degree patients were looked at (as was obtained from an additional exploration of our head orientation data). Moreover, implicit and explicit attitudes were predicted to moderate this relationship. Participants (N = 50) were healthy, heterosexual students. A main effect of diagnosis revealed larger interpersonal distances from patients with HIV than from patients with cancer. Also, an interaction effect demonstrated that distances were largest when the HIV patient was homosexual. Furthermore, a main effect of diagnosis showed that HIV and cancer patients were approached more slowly than broken leg patients, an effect that was larger for HIV than for cancer patients. In addition, head orientation analyses revealed that patients with HIV were relatively ‘looked at’ more often as well as relatively ‘looked away from’ less often than patients with cancer and patients with a broken leg. None of these effects however were found to be moderated by implicit and explicit attitudes. These findings provide behavioural evidence for the stigmatization of people living with HIV and homosexuals with HIV in particular. Copyright © 2015 John Wiley & Sons, Ltd.
Scanning Electrochemical Microscopy Applied to the Investigation of Lithium (De‐)Insertion in TiO2
Authors: Zampardi Giorgia , Ventosa Edgar , La Mantia Fabio , Schuhmann Wolfgang
Published: March 2015

The electrochemical insertion of lithium ions in anatase TiO2 nanoparticles was investigated by scanning electrochemical microscopy in the feedback mode of operation using ferrocene as reporting redox couple at different potentials in presence and absence of lithium ions. By fixing the position of the tip while performing cyclic voltammetry at the TiO2 paste electrode, the formation of the solid electrolyte interphase (SEI) on the surface of titania was followed in situ. Different scan rates have been used to study the kinetics of SEI formation.
Electron Transfer Rates in an Adsorbed C60‐Porphyrin Dyad
Authors: Fortgang Philippe , Urbani Maxence , Holler Michel , Nierengarten Jean‐François , Moreau Alain , Delavaux‐Nicot Béatrice , Maisonhaute Emmanuel
Published: March 2015

Association of C60 and porphyrin entities to build light harvesting systems is a promising alternative for future photovoltaic devices. Herein, we determine the electron transfer rates in a C60‐porphyrin dyad anchored onto a gold ultramicroelectrode via the porphyrin core. Similar rates are observed for both redox entities, suggesting a tilt of the molecules allowing an efficient through‐space communication between C60 and the electrode.
The Mechanism of Mediated Electron Transfer at Redox Active Surfaces
Authors: Lyons Michael E. G.
Published: March 2015

Theoretical models describing transport and kinetic processes involved in heterogeneous redox catalysis of solution phase reactants at RDE surfaces modified with catalytically active layers are presented. Model A regards the interaction between the surface immobilized redox active mediator and substrate being described in terms of bimolecular reaction kinetics. Model B assumes the interaction involves the formation of an adduct. Both consider the processes of heterogeneous electron transfer between immobilized mediator and support electrode, chemical reaction between redox mediator/reactant, and reactant diffusive mass transport, and expressions for the net reaction flux are derived. Kinetic case diagrams are constructed.
Electrohydrodynamically Printed, Flexible Energy Harvester Using In Situ Poled Piezoelectric Nanofibers
Authors: Ding Yajiang , Duan Yongqing , Huang YongAn
Published: March 2015

This article presents the fabrication of electrohydrodynamically printed energy harvesters based on piezoelectric polyvinylidene fluoride (PVDF) nanofibers. PVDF nanofibers with β phase formation are fabricated by mechano‐electrospinning to realize in situ electric poling and mechanical stretching. By directly depositing the poled nanofibers onto flexible or prestrained elastomeric substrates, bendable or stretchable energy harvesters with high efficiency were fabricated. The flexible energy harvesters generate electricity under bending, stretching, and compression, and the generated current is characterized by a linear ratio to the stretching frequency/strain as well as the number of fibers. Additionally, the vertical pressure enables the stretchable energy harvesters with in‐surface buckled fibers to generate electricity stably even if the harvesters exist in different stretching statuses. The printed energy harvesters pave the way for a cost‐effective, high‐efficiency manufacturing pathway in wearable, bio‐integrated electronics with large deformability.
Ambidexterity and Unit Performance: Intellectual Capital Antecedents and Cross‐Level Moderating Effects of Human Resource Practices
Authors: Kostopoulos Konstantinos C. , Bozionelos Nikos , Syrigos Evangelos
Published: March 2015

This study develops a cross‐level model examining the effects of intellectual capital facets (i.e., human, social, and organizational capital) on unit ambidexterity. Further, it proposes that organizational‐level high‐performance human resource (HPHR) practices significantly shape these effects as well as the unit ambidexterity–unit performance relationship. Hierarchical linear modeling on multisource and lagged data from a sample of 148 business units from 58 US Fortune 500 firms shows that unit human and social capital positively contributes to unit ambidexterity, unit organizational capital has a negative relationship with unit ambidexterity, and organizational HPHR practices amplify the former and mitigate the latter of these unit‐level effects. The findings also reveal that the relationship between ambidexterity and unit performance becomes stronger in organizational contexts of heightened HPHR practices. This multilevel approach increases understanding of how units achieve ambidexterity and attain related performance gains. © 2015 Wiley Periodicals, Inc.
Room Temperature Ionic Liquid‐based Electrolytes as an Alternative to Carbonate‐based Electrolytes
Authors: Yim Taeeun , Kwon Mi‐Sook , Mun Junyoung , Lee Kyu Tae
Published: March 2015

The issue of the safety of Li‐ion batteries is becoming more critical with the increase in their size for applications in large energy storage devices, such as hybrid electric vehicles (HEVs), and energy storage systems (ESSs) for smart grids. The thermal runaway of Li‐ion batteries is considered to be caused by their flammable components, such as the volatile carbonate solvents of electrolytes. Room temperature ionic liquids (RTILs) have recently received much attention because of their characteristics of non‐flammability and non‐volatility. In addition, RTILs show high ionic conductivity and a wide electrochemical stability window. Therefore, RTIL‐based electrolytes are considered one of the most promising candidates to improve the safety of Na‐ion, as well as Li‐ion batteries; indeed, RTIL‐based electrolytes have shown excellent improvements in terms of thermal stability and electrochemical performance. This review provides a comprehensive overview of selected RTIL materials, including their physicochemical and electrochemical properties. Moreover, we discuss the failure mechanisms of certain RTIL‐based electrolytes with various electrodes to suggest alternative strategies for improving their electrochemical performance.
Potential of biofluid components to modify silver nanoparticle toxicity
Authors: Murphy Anna , Sheehy Kate , Casey Alan , Chambers Gordon
Published: March 2015

Establishing realistic exposure scenarios is critical for cytotoxic investigation of silver nanoparticles (AgNP) in the gastrointestinal tract. This study investigated the potential interaction with and effect of biofluid components, namely cholic acid, deoxycholic acid and ursodeoxycholic acid, on AgNP toxicity. Two cell lines corresponding to organs related to the biofluid components were employed. These were HepG‐2 a hepatocellular carcinoma derived from liver tissue and Hep2 an epithelial cell line. Physiochemical and cytotoxic screening was performed and the ability of biofluid components to modify AgNP cytotoxicity was explored. No alteration to the physiochemical characteristics of AgNP by biofluid components was demonstrated. However, biofluid component addition resulted in alteration of AgNP toxicity. Greater reactive oxygen species induction was noted in the presence of cholic acid and deoxycholic acid. Ursodeoxycholic acid demonstrated no modification of toxicity in HepG‐2 cells; however, significant modification was noted in Hep2 cells. It is concluded that biofluid components can modify AgNP toxicity but this is dependent on the biofluid component itself and the location where it acts. Copyright © 2015 John Wiley & Sons, Ltd.
Fluorescence life‐time imaging and steady state polarization for examining binding of fluorophores to gold nanoparticles
Authors: Schwartz Shmulik , Fixler Dror , Popovtzer Rachela , Shefi Orit
Published: March 2015

Nanocomposites as multifunctional agents are capable of combing imaging and cell biology technologies. The conventional methods used for validation of the conjugation process of nanoparticles (NPs) to fluorescent molecules such as spectroscopy analysis and surface potential measurements, are not sufficient. In this paper we present a new and highly sensitive procedure that uses the combination of (1) fluorescence spectrum, (2) fluorescence lifetime, and (3) steady state fluorescence polarization measurements. We characterize and analyze gold NPs with Lucifer yellow (LY) surface coating as a model. We demonstrate the ability to differentiate between LY‐GNP (the conjugated complex) and a mixture of coated NP and free dyes. We suggest the approach for neuroscience applications where LY is used for detecting and labeling cells, studying morphology and intracellular communications.

Histograms of Fluorescence lifetime imaging (FLIM) of free LY dye (Left) in comparison to the conjugated dye to gold nanoparticles, LY‐GNP (Middle) enable the differentiation between LY‐GNP (the conjugated complex) and a mixture of coated NP and free dyes (Right).

magnified image

Histograms of Fluorescence lifetime imaging (FLIM) of free LY dye (Left) in comparison to the conjugated dye to gold nanoparticles, LY‐GNP (Middle) enable the differentiation between LY‐GNP (the conjugated complex) and a mixture of coated NP and free dyes (Right).
Preoperative intramuscular adipose tissue content is a novel prognostic predictor after hepatectomy for hepatocellular carcinoma
Authors: Hamaguchi Yuhei , Kaido Toshimi , Okumura Shinya , Ito Takashi , Fujimoto Yasuhiro , Ogawa Kohei , Mori Akira , Hammad Ahmed , Hatano Etsuro , Uemoto Shinji
Published: March 2015

Background

Sarcopenia has been shown to be an independent predictor of lower disease‐free and overall survival in various kinds of diseases. The quality of skeletal muscle has recently attracted much attention as a new parameter of sarcopenia.

Methods

We performed a retrospective analysis of 477 patients undergoing hepatectomy for hepatocellular carcinoma (HCC) between April 2005 and August 2014. The quality of skeletal muscle was evaluated by intramuscular adipose tissue content (IMAC) using preoperative computed tomography (CT) imaging. The impact of IMAC on outcomes after hepatectomy for HCC was analyzed.

Results

Patients with high IMAC showed older age, higher body mass index, higher indocyanine green retention test at 15 min, and more operative blood loss. The overall and recurrence‐free survival rates were significantly lower in patients with high IMAC than in patients with normal IMAC (P < 0.0001, P = 0.0012, respectively). Multivariate analysis showed that high IMAC was the significant risk factor for death (hazard ratio [HR] = 2.942; P < 0.0001) and for HCC recurrence (HR = 1.529; P = 0.0007) after hepatectomy.

Conclusions

Preoperative quality of skeletal muscle was closely correlated with postoperative mortality and HCC recurrence. IMAC could be incorporated into new selection criteria for hepatectomy for HCC.