bluuebunny/crossref_metadata_2025 huggingface dataset:
Development of HF radar inversion algorithm for spectrum estimation (HIAS)
Authors: Hisaki Yukiharu
Published: February 2015

A method for estimating ocean wave directional spectra using an HF (high‐frequency) ocean radar was developed. This method represents the development of work conducted in previous studies. In the present method, ocean wave directional spectra are estimated on polar coordinates whose center is the radar position, while spectra are estimated on regular grids. This method can be applied to both single and multiple radar cases. The area for wave estimation is more flexible than that of the previous method. As the signal to noise (SN) ratios of Doppler spectra are critical for wave estimation, we develop a method to exclude low SN ratio Doppler spectra. The validity of the method is demonstrated by comparing results with in situ observed wave data that it would be impossible to estimate by the methods of other groups.
Upper tropospheric ozone production from lightning NOx‐impacted convection: Smoke ingestion case study from the DC3 campaign
Authors: Apel E. C. , Hornbrook R. S. , Hills A. J. , Blake N. J. , Barth M. C. , Weinheimer A. , Cantrell C. , Rutledge S. A. , Basarab B. , Crawford J. , Diskin G. , Homeyer C. R. , Campos T. , Flocke F. , Fried A. , Blake D. R. , Brune W. , Pollack I. , Peischl J. , Ryerson T. , Wennberg P. O. , Crounse J. D. , Wisthaler A. , Mikoviny T. , Huey G. , Heikes B. , O'Sullivan D. , Riemer D. D.
Published: February 2015

As part of the Deep Convective Cloud and Chemistry (DC3) experiment, the National Science Foundation/National Center for Atmospheric Research (NCAR) Gulfstream‐V (GV) and NASA DC‐8 research aircraft probed the chemical composition of the inflow and outflow of two convective storms (north storm, NS, south storm, SS) originating in the Colorado region on 22 June 2012, a time when the High Park wildfire was active in the area. A wide range of trace species were measured on board both aircraft including biomass burning (BB) tracers hydrogen cyanide (HCN) and acetonitrile (ACN). Acrolein, a much shorter lived tracer for BB, was also quantified on the GV. The data demonstrated that the NS had ingested fresh smoke from the High Park fire and as a consequence had a higher VOC OH reactivity than the SS. The SS lofted aged fire tracers along with other boundary layer ozone precursors and was more impacted by lightning NOx (LNOx) than the NS. The NCAR master mechanism box model was initialized with measurements made in the outflow of the two storms. The NS and SS were predicted to produce 11 and 14 ppbv of O3, respectively, downwind of the storm over 2 days. Sensitivity tests revealed that the ozone production potential of the SS was highly dependent on LNOx. Normalized excess mixing ratios, ΔX/ΔCO, for HCN and ACN were determined in both the fire plume and the storm outflow and found to be 7.0 ± 0.5 and 2.3 ± 0.5 pptv ppbv−1, respectively, and 1.4 ± 0.3 pptv ppbv−1 for acrolein in the outflow only.
A reassessment of the integrated impact of tropical cyclones on surface chlorophyll in the western subtropical North Atlantic
Authors: Foltz Gregory R. , Balaguru Karthik , Leung L. Ruby
Published: February 2015

The impact of tropical cyclones on surface chlorophyll concentration is assessed in the western subtropical North Atlantic Ocean during 1998–2011. Previous studies in this area focused on individual cyclones and gave mixed results regarding the importance of tropical cyclone‐induced mixing for changes in surface chlorophyll. Using a more integrated and comprehensive approach that includes quantification of cyclone‐induced changes in mixed layer depth, here it is shown that accumulated cyclone energy explains 22% of the interannual variability in seasonally averaged (June–November) chlorophyll concentration in the western subtropical North Atlantic, after removing the influence of the North Atlantic Oscillation (NAO). The variance explained by tropical cyclones is thus about 70% of that explained by the NAO, which has well‐known impacts in this region. It is therefore likely that tropical cyclones contribute significantly to interannual variations of primary productivity in the western subtropical North Atlantic during the hurricane season.
The Effect of Gradual Fluorination on the Properties of FnZnPc Thin Films and FnZnPc/C60 Bilayer Photovoltaic Cells
Authors: Brendel Michael , Krause Stefan , Steindamm Andreas , Topczak Anna Katharina , Sundarraj Sudhakar , Erk Peter , Höhla Steffen , Fruehauf Norbert , Koch Norbert , Pflaum Jens
Published: February 2015

Motivated by the possibility of modifying energy levels of a molecule without substantially changing its band gap, the impact of gradual fluorination on the optical and structural properties of zinc phthalocyanine (FnZnPc) thin films and the electronic characteristics of FnZnPc/C60 (n = 0, 4, 8, 16) bilayer cells is investigated. UV–vis measurements reveal similar Q‐ and B‐band absorption of FnZnPc thin films with n = 0, 4, 8, whereas for F16ZnPc a different absorption pattern is detected. A correlation between structure and electronic transport is deduced. For F4ZnPc/C60 cells, the enhanced long range order supports fill factors of 55% and an increase of the short circuit current density by 18%, compared to ZnPc/C60. As a parameter being sensitive to the organic/organic interface energetics, the open circuit voltage is analyzed. An enhancement of this quantity by 27% and 50% is detected for F4ZnPc‐ and F8ZnPc‐based devices, respectively, and is attributed to an increase of the quasi‐Fermi level splitting at the donor/acceptor interface. In contrast, for F16ZnPc/C60 a decrease of the open circuit voltage is observed. Complementary photoelectron spectroscopy, external quantum efficiency, and photoluminescence measurements reveal a different working principle, which is ascribed to the particular energy level alignment at the interface of the photoactive materials.
Gold(I)/Copper(II)‐Cocatalyzed Tandem Cyclization/Semipinacol Reaction: Construction of 6‐Aza/Oxa‐Spiro[4.5]decane Skeletons and Formal Synthesis of (±)‐Halichlorine
Authors: Zhu Dao‐Yong , Zhang Zhen , Mou Xue‐Qing , Tu Yong‐Qiang , Zhang Fu‐Min , Peng Jin‐Bao , Wang Shao‐Hua , Zhang Shu‐Yu
Published: February 2015

A simple and efficient strategy for the construction of 6‐aza/oxa‐spiro[4.5]decane skeletons under the cocatalysis of gold(I)/copper(II) was developed, and its potential utility was demonstrated by a formal synthesis of the biologically active marine alkaloid (±)‐halichlorine.

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Copper‐Mediated ortho‐Nitration of Arene and Heteroarene CH Bonds Assisted by an 8‐Aminoquinoline Directing Group
Authors: Liu Jidan , Zhuang Shaobo , Gui Qingwen , Chen Xiang , Yang Zhiyong , Tan Ze
Published: February 2015

A copper‐mediated, chelation‐assisted ortho CH bond nitration of benzoic acid derivatives using sodium nitrite as the source of the nitro group has been achieved with the aid of an 8‐aminoquinoline directing group. Selective mono‐ or dinitration can be achieved by simply changing the reaction conditions. The method shows excellent functional group tolerance and provides a novel and straightforward route for the preparation of ortho‐nitrated benzoic acids.

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Copper Chloride‐Catalyzed Aerobic Oxidative Annulation of N‐Furfuryl‐β‐Enaminones:Access to Polysubstituted Pyrroles and Indoles
Authors: Liu Jianchao , Zhang Xiaoting , Peng Hui , Jiang Huanfeng , Yin Biaolin
Published: February 2015

Copper chloride‐catalyzed aerobic oxidative annulation of N‐furfuryl‐β‐enaminones provides access to polysubstituted pyrroles and indoles. This protocol involves an unprecedented copper chloride‐catalyzed oxidative chlorination of furan and pyrrole rings with oxygen as the terminal oxidant.

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Analysis of CHRNA7 rare variants in autism spectrum disorder susceptibility
Authors: Bacchelli Elena , Battaglia Agatino , Cameli Cinzia , Lomartire Silvia , Tancredi Raffaella , Thomson Susanne , Sutcliffe James S , Maestrini Elena
Published: February 2015

Chromosome 15q13.3 recurrent microdeletions are causally associated with a wide range of phenotypes, including autism spectrum disorder (ASD), seizures, intellectual disability, and other psychiatric conditions. Whether the reciprocal microduplication is pathogenic is less certain. CHRNA7, encoding for the alpha7 subunit of the neuronal nicotinic acetylcholine receptor, is considered the likely culprit gene in mediating neurological phenotypes in 15q13.3 deletion cases. To assess if CHRNA7 rare variants confer risk to ASD, we performed copy number variant analysis and Sanger sequencing of the CHRNA7 coding sequence in a sample of 135 ASD cases. Sequence variation in this gene remains largely unexplored, given the existence of a fusion gene, CHRFAM7A, which includes a nearly identical partial duplication of CHRNA7. Hence, attempts to sequence coding exons must distinguish between CHRNA7 and CHRFAM7A, making next‐generation sequencing approaches unreliable for this purpose. A CHRNA7 microduplication was detected in a patient with autism and moderate cognitive impairment; while no rare damaging variants were identified in the coding region, we detected rare variants in the promoter region, previously described to functionally reduce transcription. This study represents the first sequence variant analysis of CHRNA7 in a sample of idiopathic autism. © 2015 Wiley Periodicals, Inc.
Phenotypic sub‐grouping in microtia using a statistical and a clinical approach
Authors: Luquetti Daniela V. , Saltzman Babette S. , Heike Carrie L. , Sie Kathleen C. , Birgfeld Craig B. , Evans Kelly N. , Leroux Brian G.
Published: February 2015

The clinical presentation of microtia varies widely from minimal morphological abnormalities to complete absence of the ear. In this study we sought to identify and characterize sub‐groups of microtia using a statistical and a clinical approach. Photographs of 86 ears were classified in relation to all the external ear components. We used cluster analysis and rater's clinical opinion to identify groups with similar phenotypes in two separate analyses. We used Cramer's Phi coefficient of association to assess the similarity among the clinician's groupings as well as among the statistical sub‐phenotypic groups and each of the clinician's groupings. The cluster analysis initially divided the 86 ears into a more and a less severe group. The less severe group included two sub‐groups that included ears classified as normal and a group that had very few anomalous components. The group of 48 more affected ears all had abnormalities of the helix crus; antihelix‐stem, ‐superior crus and ‐inferior crus; and antitragus. These were further divided into 4 sub‐phenotypes. There was a moderate degree of association among the raters' groupings (Cramer's Phi: 0.64 to 0.73). The statistical and clinical groupings had a lower degree of association (Cramer's Phi: 0.49 to 0.58). Using standardized characterization of structural abnormalities of the ear we identified six distinct phenotypic groups; correlations with clinicians' groupings were moderate. These clusters may represent groups of ear malformations associated with the same etiology, similar time of insult or target cell population during embryonic development. The results will help inform investigations on etiology. © 2015 Wiley Periodicals, Inc.
The relationship between schizophrenia and rheumatoid arthritis revisited: Genetic and epidemiological analyses
Authors: Euesden Jack , Breen Gerome , Farmer Anne , McGuffin Peter , Lewis Cathryn M
Published: February 2015

Epidemiological studies are inconsistent on the relationship between schizophrenia (SCZ) and rheumatoid arthritis (RA). Several studies have shown that SCZ has a protective effect on RA, with RA occurring less frequently in SCZ cases than would be expected by chance, whilst other studies have failed to replicate this. We sought to test the hypothesis that this effect is due to a protective effect of SCZ risk alleles on RA onset. We first reviewed the literature on the comorbidity of RA and SCZ and performed a meta‐analysis. We then used polygenic risk scoring in an RA case control study in order to investigate the contribution of SCZ risk alleles to RA risk. Meta‐analysis across studies over the past half‐century showed that prevalence of RA in SCZ cases was significantly reduced (OR = 0.48, 95% CI: 0.34–0.67, p  < 0.0001). The relationship between SCZ genetic risk and RA status was weak. Polygenic risk of SCZ explained a small (0.1%) and non‐significant (p = 0.085) proportion of variance in RA case control status. This relationship was nominally positive, with RA cases carrying more SCZ risk alleles than controls. The current findings do not support the assertion that the relationship between RA and SCZ is explained by genetic factors, which appear to have little or no effect. The protective effect of SCZ on RA may be due to environmental factors, such as an anti‐inflammatory effect of anti‐psychotic medication or merely due to confounding limitations in study designs. © 2015 The Authors. American Journal of Medical Genetics Part B: Neuropsychiatric Genetics published by Wiley Periodicals, Inc.
An association between a dopamine transporter gene (SLC6A3) haplotype and ADHD symptom measures in nonclinical adults
Authors: Tong Janette H.S. , Cummins Tarrant D.R. , Johnson Beth P. , McKinley Leigh‐Anne , Pickering Hayley E. , Fanning Peter , Stefanac Nicole R. , Newman Daniel P. , Hawi Ziarih , Bellgrove Mark A.
Published: February 2015

Previous genetic studies have postulated that attention deficit hyperactivity disorder (ADHD) should be regarded as the extreme end of a set of behavioural traits that can be continuously measured in the general population. The current study adopted a quantitative trait approach to examine the relationship between dopamine gene variants and self‐reported ADHD symptoms in 517 nonclinical adults. Although genetic associations with variants of both the dopamine transporter (DAT1; SLC6A3) and D4 receptor (DRD4) genes have been reliably reported in children, results in adults are less consistent. We probed two potentially functional variable number of tandem repeat (VNTR) polymorphisms in the 3′UTR and intron 8 of DAT1, the 10‐repeat and 6‐repeat alleles of which respectively form a haplotype (10/6 DAT1 haplotype) that is associated with childhood ADHD. We also genotyped the exon 3 VNTR of DRD4, the 7‐repeat allele of which is also an established risk factor for childhood ADHD. Permutation analysis showed an influence of the 10/6 DAT1 haplotype on both CAARS‐G and CAARS‐H (DSM‐IV ADHD Symptoms Total and ADHD Index respectively), such that ADHD symptom scores increased with each additional copy of the 10/6 DAT1 haplotype. This result survived corrections for multiple comparisons both at the level of genotype and phenotype. A nominal association with CAARS‐G was also found for the 7‐repeat allele of the DRD4 VNTR however this did not survive multiple comparison correction. Our results provide further support for the influence of variation in the 10/6 DAT1 haplotype and individual differences in ADHD symptoms in adults. © 2015 Wiley Periodicals, Inc.
A preliminary analysis of microRNA as potential clinical biomarker for schizophrenia
Authors: Sun Xin‐yang , Zhang Jin , Niu Wei , Guo Wei , Song Hong‐tao , Li Heng‐yu , Fan Hui‐min , Zhao Lin , Zhong Ai‐fang , Dai Yun‐hua , Guo Zhong‐min , Zhang Li‐yi , Lu Jim , Zhang Qiao‐li
Published: February 2015

MicroRNAs (miRNA, miR) have been implicated as promising blood‐based biomarkers for schizophrenia patients. This study aimed to clinically validate miRNA as potential schizophrenia biomarkers. Plasma levels of 10 miRNAs were analyzed using qPCR in a cohort of 61 schizophrenia patients and 62 normal controls, as well as 25 patients particularly selected for a six‐week antipsychotic treatment course. Positive And Negative Syndrome Scale (PANSS), Global Assessment Scale (GAS) and Clinical Global Impression (CGI) were administered to assess the clinical symptoms. The results demonstrated that a panel of miRNAs consisting of miR‐30e, miR‐181b, miR‐34a, miR‐346 and miR‐7 had significantly increased expression levels with significant combined diagnostic value (AUC:0.713; sensitivity:35.5%; specificity:90.2%). In response to pharmacological treatment, expression levels of miR‐132, miR‐181b, miR‐432 and miR‐30e were significantly decreased. In addition, the improvement of clinical symptomatology was significantly correlated with the changes of miR‐132, miR‐181b, miR‐212 and miR‐30e expression levels. Furthermore, the decreases of plasma levels of miR‐132 and miR‐432 were significantly greater in high‐effect subgroup than those in low‐effect subgroup after six‐week treatment course. We conclude that miR‐30e, miR‐181b, miR‐34a, miR‐346 and miR‐7 combined as a panel are potentially useful non‐invasive biomarkers for schizophrenia diagnosis. Markers miR‐132, miR‐181b, miR‐30e and miR‐432 are potential indicators for symptomatology improvements, treatment responses and prognosis for schizophrenia patients. © 2015 Wiley Periodicals, Inc.
Neurodevelopmental attributes of joint hypermobility syndrome/Ehlers–Danlos syndrome, hypermobility type: Update and perspectives
Authors: Ghibellini Giulia , Brancati Francesco , Castori Marco
Published: February 2015

In the last decade, increasing attention has been devoted to the extra‐articular and extra‐cutaneous manifestations of joint hypermobility syndrome, also termed Ehlers–Danlos syndrome, hypermobility type (i.e., JHS/EDS‐HT). Despite the fact that the current diagnostic criteria for both disorders remain focused on joint hypermobility, musculoskeletal pain and skin changes, medical practice and research have started investigating a wide spectrum of visceral, neurological and developmental complications, which represent major burdens for affected individuals. In particular, children with generalized joint hypermobility often present with various neurodevelopmental issues and can be referred for neurological consultation. It is common that investigations in these patients yield negative or inconsistent results, eventually leading to the exclusion of any structural neurological or muscle disorder. In the context of specialized clinics for connective tissue disorders, a clear relationship between generalized joint hypermobility and a characteristic neurodevelopmental profile affecting coordination is emerging. The clinical features of these patients tend to overlap with those of developmental coordination disorder and can be associated with learning and other disabilities. Physical and psychological consequences of these additional difficulties add to the chief manifestations of the pre‐existing connective tissue disorder, affecting the well‐being and development of children and their families. In this review, particular attention is devoted to the nature of the link between joint hypermobility, coordination difficulties and neurodevelopmental issues in children. Presumed pathogenesis and management issues are explored in order to attract more attention on this association and nurture future clinical research. © 2015 Wiley Periodicals, Inc.
Spectrum of mucocutaneous manifestations in 277 patients with joint hypermobility syndrome/Ehlers‐Danlos syndrome, hypermobility type
Authors: Castori Marco , Dordoni Chiara , Morlino Silvia , Sperduti Isabella , Ritelli Marco , Valiante Michele , Chiarelli Nicola , Zanca Arianna , Celletti Claudia , Venturini Marina , Camerota Filippo , Calzavara‐Pinton Piergiacomo , Grammatico Paola , Colombi Marina
Published: February 2015

Cutaneous manifestations are a diagnostic criterion of Ehlers–Danlos syndrome, hypermobility type (EDS‐HT) and joint hypermobility syndrome (JHS). These two conditions, originally considered different disorders, are now accepted as clinically indistinguishable and often segregate as a single‐familial trait. EDS‐HT and JHS are still exclusion diagnoses not supported by any specific laboratory test. Accuracy of clinical diagnosis is, therefore, crucial for appropriate patients' classification and management, but it is actually hampered by the low consistency of many applied criteria including the cutaneous one. We report on mucocutaneous findings in 277 patients with JHS/EDS‐HT with both sexes and various ages. Sixteen objective and five anamnestic items were selected and ascertained in two specialized outpatient clinics. Feature rates were compared by sex and age by a series of statistical tools. Data were also used for a multivariate correspondence analysis with the attempt to identify non‐causal associations of features depicting recognizable phenotypic clusters. Our findings identified a few differences between sexes and thus indicated an attenuated sexual dimorphism for mucocutaneous features in JHS/EDS‐HT. Ten features showed significantly distinct rates at different ages and this evidence corroborated the concept of an evolving phenotype in JHS/EDS‐HT also affecting the skin. Multivariate correspondence analysis identified three relatively discrete phenotypic profiles, which may represent the cutaneous counterparts of the three disease phases previously proposed for JHS/EDS‐HT. These findings could be used for revising the cutaneous criterion in a future consensus for the clinical diagnosis of JHS/EDS‐HT. © 2015 Wiley Periodicals, Inc.
Localized Template‐Driven Functionalization of Nanoparticles by Dynamic Combinatorial Chemistry
Authors: Nowak Piotr , Saggiomo Vittorio , Salehian Fatemeh , Colomb‐Delsuc Mathieu , Han Yang , Otto Sijbren
Published: February 2015

We have developed a method for the localized functionalization of gold nanoparticles using imine‐based dynamic combinatorial chemistry. By using DNA templates, amines were grafted on the aldehyde‐functionalized nanoparticles only if and where the nanoparticles interacted with the template molecules. Functionalization of the nanoparticles was controlled solely by the DNA template; only amines capable of interacting with DNA were bound to the surface. Interestingly, even though our libraries contained only a handful of simple amines, the DNA sequence influenced their attachment to the surface. Our method opens up new opportunities for the synthesis of multivalent, nanoparticle‐based receptors for biomacromolecules.
Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen‐Doped Carbon Composites For High‐Performance Lithium–Sulfur Battery Cathodes
Authors: Song Jiangxuan , Gordin Mikhail L. , Xu Terrence , Chen Shuru , Yu Zhaoxin , Sohn Hiesang , Lu Jun , Ren Yang , Duan Yuhua , Wang Donghai
Published: February 2015

Despite the high theoretical capacity of lithium–sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon‐nanotube‐interpenetrated mesoporous nitrogen‐doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g−1 after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer‐sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm−2) with a high sulfur loading of approximately 5 mg cm−2, which is ideal for practical applications of the lithium–sulfur batteries.
Water‐Soluble Triazabutadienes that Release Diazonium Species upon Protonation under Physiologically Relevant Conditions
Authors: Kimani Flora W. , Jewett John C.
Published: February 2015

Triazabutadienes are an understudied structural motif that have remarkable reactivity once rendered water‐soluble. It is shown that these molecules readily release diazonium species in a pH‐dependent manner in a series of buffer solutions with pH ranges similar to those found in cells. Upon further development, we expect that this process will be well suited to cargo‐release strategies and organelle‐specific bioconjugation reactions. These compounds offer one of the mildest ways of generating diazonium species in aqueous solutions.
High‐Contrast Red–Green–Blue Tricolor Fluorescence Switching in Bicomponent Molecular Film
Authors: Kim Hyeong‐Ju , Whang Dong Ryeol , Gierschner Johannes , Lee Chong Han , Park Soo Young
Published: February 2015

Highly efficient red–green–blue (RGB) tricolor luminescence switching was demonstrated in a bicomponent solid film consisting of (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(4‐butoxyphenyl)acrylonitrile) (DBDCS) and (2Z,2′Z)‐3,3′‐(2,5‐bis(6‐(9H‐carbazol‐9‐yl)hexyloxy)‐1,4‐phenylene)bis(2‐(3,5‐bis(trifluoromethyl)phenyl)acrylonitrile) (m‐BHCDCS). Reversible RGB luminescence switching with a high ratiometric color contrast (λem=594, 527, 458 nm for red, green, and blue, respectively) was realized by different external stimuli such as heat, solvent vapor exposure, and mechanical force. It was shown that Förster resonance energy transfer in the bicomponent mixture could be efficiently switched on and off through supramolecular control.
Mangankatalysierte Synthese von cis‐β‐Aminosäureestern mittels metallorganischer C‐H‐Aktivierung von Ketiminen
Authors: Liu Weiping , Zell Daniel , John Michael , Ackermann Lutz
Published: February 2015

Mangankatalysierte C‐H‐Funktionalisierungen von Ketiminen schaffen die Voraussetzung für die Synthese von cis‐β‐Aminosäureestern mittels regio‐ und stereoselektiver Alkenanellierung. Die metallorganische C‐H‐Aktivierung weist eine gute Toleranz gegenüber funktionellen Gruppen auf und liefert hochfunktionalisierte β‐Aminosäurederivate mit großer Substratbreite.
Manganese‐Catalyzed Synthesis of cis‐β‐Amino Acid Esters through Organometallic CH Activation of Ketimines
Authors: Liu Weiping , Zell Daniel , John Michael , Ackermann Lutz
Published: February 2015

Manganese‐catalyzed CH functionalization reactions of ketimines set the stage for the expedient synthesis of cis‐β‐amino acid esters through site‐ and regioselective alkene annulations. The organometallic CH activation occurred efficiently with high functional group tolerance, delivering densely functionalized β‐amino acid derivatives with ample scope.
Electron‐Induced Hydration of an Alkene: Alternative Reaction Pathways
Authors: Warneke Jonas , Wang Ziyan , Swiderek Petra , Bredehöft Jan Hendrik
Published: February 2015

Electron‐induced reactions in condensed mixtures of ethylene and water lead to the synthesis of ethanol, as shown by post‐irradiation thermal desorption spectrometry (TDS). Interestingly, this synthesis is not only induced by soft electron impact ionization similar to a previously observed electron‐induced hydroamination but also, at low electron energy, by electron attachment to ethylene and a subsequent acid/base reaction with water.
Photochemical Internalization of Tamoxifens Transported by a “Trojan‐Horse” Nanoconjugate into Breast‐Cancer Cell Lines
Authors: Theodossiou Theodossis A. , Gonçalves A. Ricardo , Yannakopoulou Konstantina , Skarpen Ellen , Berg Kristian
Published: February 2015

Photochemical internalization (PCI) has shown great promise as a therapeutic alternative for targeted drug delivery by light‐harnessed activation. However, it has only been applicable to therapeutic macromolecules or medium‐sized molecules. Herein we describe the use of an amphiphilic, water‐soluble porphyrin–β‐cyclodextrin conjugate (mTHPP‐βCD) as a “Trojan horse” to facilitate the endocytosis of CD‐guest tamoxifens into breast‐cancer cells. Upon irradiation, the porphyrin core of mTHPP‐βCD expedited endosomal membrane rupture and tamoxifen release into the cytosol, as documented by confocal microscopy. The sustained complexation of mTHPP‐βCD with tamoxifen was corroborated by 2D NMR spectroscopy and FRET studies. Following the application of PCI protocols with 4‐hydroxytamoxifen (4‐OHT), estrogen‐receptor β‐positive (Erβ+, but not ERβ−) cell groups exhibited extensive cytotoxicity and/or growth suspension even at 72 h after irradiation.
Geometric and Electronic Structures of Boron(III)‐Cored Dyes Tailored by Incorporation of Heteroatoms into Ligands
Authors: Sun Lin , Zhang Fan , Wang Xinyang , Qiu Feng , Xue Minzhao , Tregnago Giulia , Cacialli Franco , Osella Silvio , Beljonne David , Feng Xinliang
Published: February 2015

Complexation of a boron atom with a series of bidentate heterocyclic ligands successfully gives rise to corresponding BF2‐chelated heteroarenes, which could be considered as novel boron(III)‐cored dyes. These dye molecules exhibit planar structures and expanded π‐conjugated backbones due to the locked conformation with a boron center. The geometric and electronic structures of these BF2 complexes can be tailored by embedding heteroatoms in the unique modes to form positional isomer and isoelectronic structures. The structure–property relationship is further elucidated by studying the photophysical properties, electrochemical behavior and quantum‐chemical calculations.
Exogenous retinoic acid induces digit reduction in opossums (Monodelphis domestica) by disrupting cell death and proliferation, and apical ectodermal ridge and zone of polarizing activity function
Authors: Molineaux Anna C. , Maier Jennifer A. , Schecker Teresa , Sears Karen E.
Published: February 2015

Background

Retinoic acid (RA) is a vitamin A derivative. Exposure to exogenous RA generates congenital limb malformations (CLMs) in species from frogs to humans. These CLMs include but are not limited to oligodactyly and long‐bone hypoplasia. The processes by which exogenous RA induces CLMs in mammals have been best studied in mouse, but as of yet remain unresolved.

Methods

We investigated the impact of exogenous RA on the cellular and molecular development of the limbs of a nonrodent model mammal, the opossum Monodelphis domestica. Opossums exposed to exogenous retinoic acid display CLMs including oligodactly, and results are consistent with opossum development being more susceptible to RA‐induced disruptions than mouse development.

Results

Exposure of developing opossums to exogenous RA leads to an increase in cell death in the limb mesenchyme that is most pronounced in the zone of polarizing activity, and a reduction in cell proliferation throughout the limb mesenchyme. Exogenous RA also disrupts the expression of Shh in the zone of polarizing activity, and Fgf8 in the apical ectodermal ridge, and other genes with roles in the regulation of limb development and cell death.

Conclusion

Results are consistent with RA inducing CLMs in opossum limbs by disrupting the functions of the apical ectodermal ridge and zone of polarizing activity, and driving an increase in cell death and reduction of cell proliferation in the mesenchyme of the developing limb. Birth Defects Research (Part A) 103:225–234, 2015. © 2015 Wiley Periodicals, Inc.
CRAC channel is inhibited by neomycin in a Ptdlns(4,5)P2‐independent manner
Authors: Huang Kun , Wang Xuemei , Liu Yanjun , Zhao Yi
Published: February 2015

Depletion of intracellular Ca2+ stores evokes store‐operated Ca2+ entry through the Ca2+ release‐activated Ca2+ (CRAC) channels. In this study, we found that the store‐operated Ca2+ entry was inhibited by neomycin, an aminoglycoside that strongly binds phosphatidylinositol 4,5‐bisphosphate (PtdIns(4,5)P2). Patch clamp recordings revealed that neomycin blocked the CRAC currents reconstituted by co‐expression of Orai1 and Stim1 in HEK293 cells. Using a rapamycin‐inducible PtdIns(4,5)P2‐specific phosphatase (Inp54p) system to manipulate the PtdIns(4,5)P2 in the plasma membrane, we found that the CRAC current was not altered by PtdIns(4,5)P2 depletion. This result suggests that PtdIns(4,5)P2 is not required for CRAC channel activity, and thereby, neomycin inhibits CRAC channels in a manner that is independent of neomycin–PtdIns(4,5)P2 binding. Copyright © 2015 John Wiley & Sons, Ltd.
Loss of EGF‐dependent cell proliferation ability on radioresistant cell HepG2‐8960‐R
Authors: Saito Yohei , Abiko Ryo , Kishida Akira , Kuwahara Yoshikazu , Yamamoto Yumi , Yamamoto Fumihiko , Fukumoto Manabu , Ohkubo Yasuhito
Published: February 2015

Acquired radioresistance of cancer cells interferes with radiotherapy and increases the probability of cancer recurrence. HepG2‐8960‐R, which is one of several clinically relevant radioresistant (CRR) cell lines, has a high tolerance to the repeated clinically relevant doses of X‐ray radiation. In this study, HepG2‐8960‐R had slightly lower cell proliferation ability than HepG2 in the presence of FBS. In particular, epidermal growth factor (EGF) hardly enhanced cell proliferation and DNA synthesis in HepG2‐8960‐R. Additionally, EGF could not induce the activation of Erk1/2, because the expression of EGF receptor (EGFR) protein decreased in HepG2‐8960‐R in accordance with the methylation of the EGFR promoter region. Therefore, cetuximab did not inhibit HepG2‐8960‐R cell proliferation. Our study showed that HepG2‐8960‐R had radioresistant and cetuximab‐resistant abilities. Copyright © 2015 John Wiley & Sons, Ltd.
Synthesis and Analysis of Specific Covalent Inhibitors of endo‐Xyloglucanases
Authors: Fenger Thomas Hauch , Brumer Harry
Published: February 2015

A series of N‐bromoacetylglycosylamines and bromoketone C‐glycosides were synthesised from complex xyloglucan oligosaccharide (XyGO) scaffolds as specific active‐site affinity labels for endo‐xyloglucanases. Compounds based on XXXG (Xyl3Glc4) and XLLG (Xyl3Glc4Gal2) oligosaccharides exhibited strikingly higher affinities and higher rates of irreversible inhibition than known cellobiosyl and new lactosyl disaccharide congeners when tested with endo‐xyloglucanases from two distinct glycoside hydrolase (GH) families. Intact‐protein mass spectrometry indicated that inactivation with XyGO derivatives generally resulted in a 1:1 labelling stoichiometry. Together, these results indicate that XyGO‐based affinity reagents have significant potential as inhibitors and proteomic reagents for the identification and analysis of diverse xyloglucan‐active enzymes in nature, to facilitate industrial enzyme applications.
Nickel–Aluminum Intermetallic Compounds as Highly Selective and Stable Catalysts for the Hydrogenation of Naphthalene to Tetralin
Authors: Chen Xiao , Ma Yue , Wang Lei , Yang Zonghan , Jin Shaohua , Zhang Liangliang , Liang Changhai
Published: February 2015

Selective hydrogenation of naphthalene to tetralin was conducted by using Ni–Al intermetallic compounds (IMCs) prepared by a chemical synthetic route. Ni–Al IMC catalysts achieved a lasting high conversion with 100 % selectivity up to 125 h. During the synthesis process, the Ni–Al IMCs underwent the following phase transformation as a function of the content of the Al source (LiAlH4): Ni(cubic)→Ni3Al(tetragonal)→NiAl(cubic)→Ni2Al3(hexagonal). In the selective hydrogenation of naphthalene, the catalytic activity of NiAl was much higher than that of metallic Ni and other Ni–Al IMCs (Ni3Al and Ni2Al3). The results can be understood by a combination of site isolation and alteration of the electronic structure by chemical bonding. Ni atoms are scattered and spatially isolated by Al atoms, which in turn resists carbon deposition. The findings provide a useful approach to tailor the catalytic properties of transition metals by formation of IMCs, which could be applicable in heterogeneous catalysis.
Tuning the Optical Properties of 2‐Thienylpyridyl Iridium Complexes through Carboranes and Anions
Authors: Zhu Lin , Tang Xiao , Yu Qi , Lv Wen , Yan Hong , Zhao Qiang , Huang Wei
Published: February 2015

2‐Thienylpyridyl iridium(III) complexes containing an o‐, m‐, or p‐carboranylvinyl‐2,2′‐bipyridine ligand and various counteranions (denoted o‐PF6, m‐BF4, m‐PF6, m‐SbF6, m‐ClO4, m‐OTf, m‐NO3, m‐BPh4, m‐F, m‐Cl, and p‐PF6) were synthesized by using C‐formyl carboranes as starting materials. The solid‐state structures of o‐PF6, m‐PF6, m‐ClO4, and m‐BF4 showed that the cations form twisted cavities in which the anions are fixed by multiple hydrogen bonds. Anion–hydrogen interactions were investigated for nine m‐carborane‐based complexes with different counteranions. All carborane‐based iridium(III) complexes show similar phosphorescence yields in solution but significantly different emission in the solid state. Anion‐exchange titration and theoretical calculations revealed the relationships between structures and optical properties. The size of the anion and CH⋅⋅⋅X anion–hydrogen bonds strongly influence the phosphorescence quantum yield in the solid state. In particular, the CcarH⋅⋅⋅X hydrogen bonds between the carboranyl unit and the anion play an important role in solid‐state phosphorescence. Complex p‐PF6 was successfully applied in phosphorescence‐lifetime bioimaging owing to its low toxicity and near‐infrared emission.
Thermally Triggered Solid‐State Single‐Crystal‐to‐Single‐Crystal Structural Transformation Accompanies Property Changes
Authors: Li Quan‐Quan , Ren Chun‐Yan , Huang Yang‐Yang , Li Jian‐Li , Liu Ping , Liu Bin , Liu Yang , Wang Yao‐Yu
Published: February 2015

The 1D complex [(CuL0.5H2O)⋅H2O]n (1) (H4L=2,2′‐bipyridine‐3,3′,6,6′‐tetracarboxylic acid) undergoes an irreversible thermally triggered single‐crystal‐to‐single‐crystal (SCSC) transformation to produce the 3D anhydrous complex [CuL0.5]n (2). This SCSC structural transformation was confirmed by single‐crystal X‐ray diffraction analysis, thermogravimetric (TG) analysis, powder X‐ray diffraction (PXRD) patterns, variable‐temperature powder X‐ray diffraction (VT–PXRD) patterns, and IR spectroscopy. Structural analyses reveal that in complex 2, though the initial 1D chain is still retained as in complex 1, accompanied with the Cu‐bound H2O removed and new O(carboxyl)Cu bond forming, the coordination geometries around the CuII ions vary from a distorted trigonal bipyramid to a distorted square pyramid. With the drastic structural transition, significant property changes are observed. Magnetic analyses show prominent changes from antiferromagnetism to weak ferromagnetism due to the new formed Cu1‐O‐C‐O‐Cu4 bridge. The catalytic results demonstrate that, even though both solid‐state materials present high catalytic activity for the synthesis of 2‐imidazolines derivatives and can be reused, the activation temperature of complex 1 is higher than that of complex 2. In addition, a possible pathway for the SCSC structural transformations is proposed.
Characterization for Li3PO4 catalysts toward elucidation of crystalline form and performance relationship
Authors: Ma Weihua , Li Hao , Jiang Wei , Bai Huaping , Qu Hongxia , Lu Lude
Published: February 2015

Alkaline lithium phosphates were prepared at different calcination temperatures and their catalytic properties were evaluated. The results showed that the 320 °C‐calcined lithium phosphate had the highest selectivity to allyl alcohol (AA) and higher propylene oxide (PO) conversion among those catalysts calcined from 320 °C to 800 °C. There were two forms of lithium phosphates, β‐form and γ‐form, and the transition temperature was 670 °C. The Brunauer‐Emmet‐Teller (BET) surface area and alkalinity of the β‐Li3PO4 was larger than that of the γ‐Li3PO4, and the change of the crystal forms affected catalytic activity a lot. Infrared spectra (IR) and X‐ray powder diffraction (XRD) results showed that the reason of catalyst deactivation might be related to the carbon deposits and the arrangement of the atoms in the two forms of lithium phosphates. Based on structural analysis for Li3PO4, a new mechanism of PO isomerization was proposed.
Processing the image gradient field using a topographic primal sketch approach
Authors: Gambaruto A. M.
Published: February 2015

The spatial derivatives of the image intensity provide topographic information that may be used to identify and segment objects. The accurate computation of the derivatives is often hampered in medical images by the presence of noise and a limited resolution. This paper focuses on accurate computation of spatial derivatives and their subsequent use to process an image gradient field directly, from which an image with improved characteristics can be reconstructed. The improvements include noise reduction, contrast enhancement, thinning object contours and the preservation of edges.

Processing the gradient field directly instead of the image is shown to have numerous benefits. The approach is developed such that the steps are modular, allowing the overall method to be improved and possibly tailored to different applications. As presented, the approach relies on a topographic representation and primal sketch of an image.

Comparisons with existing image processing methods on a synthetic image and different medical images show improved results and accuracy in segmentation. Here, the focus is on objects with low spatial resolution, which is often the case in medical images. The methods developed show the importance of improved accuracy in derivative calculation and the potential in processing the image gradient field directly. Copyright © 2015 John Wiley & Sons, Ltd.
Appearance, motion, and embodiment: unpacking avatars by fine‐grained communication analysis
Authors: Tanaka Kazuaki , Nakanishi Hideyuki , Hiroshi Ishiguro
Published: February 2015

Thanks to the maturity of motion tracking technologies, it became easy and inexpensive to use avatars that reflect the user's facial and body motions in real time. There is a possibility that those real‐time avatars can serve as a substitute for videos in distant communication. We conducted two experiments to confirm positive effects of avatars on distant communication. In the first experiment, the subjects watched a conversation partner's video, avatar, photo, or nothing when speaking to the partner. Because the video and avatar delivered the partner's motion while the video and photo delivered the partner's appearance, we were able to observe the effects of the motion and appearance separately. As a result, we found that presenting the motion via a video or an avatar increased the degree of the smoothness of speaking to the partner, but the appearance did not significantly affect such an influence. In the second experiment, we compared the avatar and teleoperated robot to find how a physical embodiment influences the degree of the smoothness of speech. Teleoperated robots resemble avatars in transmitting the user's body motions without disclosing the user's appearance but differ in reflecting these motions onto a robot that has a physical embodiment. We predicted that the robot produces smoother speech because the physical embodiment might make the body motions recognizable. However, the robot decreased the degree of the smoothness of speech against our expectation. The results of these experiments showed that real‐time avatars that present only body motions are enough to smooth distant communication. Copyright © 2014 John Wiley & Sons, Ltd.
Metal–Inorganic–Organic Matrices as Efficient Sorbents for Hydrogen Storage
Authors: Azzouz Abdelkrim , Nousir Saadia , Bouazizi Nabil , Roy René
Published: February 2015

Stabilization of metal nanoparticles (MNPs) without re‐aggregation is a major challenge. An unprecedented strategy is developed for achieving high dispersion of copper(0) or palladium(0) on montmorillonite‐supported diethanolamine or thioglycerol. This results in novel metal–inorganic–organic matrices (MIOM) that readily capture hydrogen at ambient conditions, with easy release under air stream. Hydrogen retention appears to involve mainly physical interactions, slightly stronger on thioglycerol‐based MIOM (S‐MIOM). Thermal enhancement of desorption suggests also a contribution of chemical interactions. The increase of hydrogen uptake with prolonged contact times arises from diffusion hindrance, which appears to be beneficial by favoring hydrogen entrapment. Even with compact structures, MIOMs act as efficient sorbents with much higher efficiency factor (1.14–1.17 mmol m−2) than many other sophisticated adsorbents reported in the literature. This opens new prospects for hydrogen storage and potential applications in microfluidic hydrogenation reactions.
FPN‐SAODV: using fuzzy petri nets for securing AODV routing protocol in mobile Ad hoc network
Authors: Pouyan Ali A. , Yadollahzadeh Tabari Meisam
Published: February 2015

In this paper, we use fuzzy Petri nets (FPNs) to propose a secure routing protocol in mobile ad hoc network. The proposed method is based on secure ad hoc on‐demand distance vector (SAODV), which is named FPN‐SAODV. In FPN‐SAODV routing protocol, for each packet delivery or firing each transition, a type of bidirectional node‐to‐node fuzzy security verification is conducted that can be carried out with five security threshold levels. This inference uses four fuzzy variables that have been selected to well represent the malicious behaviors of some public attacks in mobile ad hoc network. Furthermore, a through route security verification has been used for selecting the most secure route among each candidate path through source node to destination. Both of these verifications utilize FPN inherent features for their operation. For evaluation purpose, we used the metrics such as packet delivery ratio, end‐to‐end delay, average security level of the nodes, and percentage of true/false detector nodes. These metrics have been used for investigating the inner operation of FPN‐SAODV as determining the proper level of security threshold level in node‐to‐node security verification module. Also, these are used for comparison of FPN‐SAODV performance versus the original AODV. Copyright © 2015 John Wiley & Sons, Ltd.
Physiological ecology meets climate change
Authors: Bozinovic Francisco , Pörtner Hans‐Otto
Published: February 2015

In this article, we pointed out that understanding the physiology of differential climate change effects on organisms is one of the many urgent challenges faced in ecology and evolutionary biology. We explore how physiological ecology can contribute to a holistic view of climate change impacts on organisms and ecosystems and their evolutionary responses. We suggest that theoretical and experimental efforts not only need to improve our understanding of thermal limits to organisms, but also to consider multiple stressors both on land and in the oceans. As an example, we discuss recent efforts to understand the effects of various global change drivers on aquatic ectotherms in the field that led to the development of the concept of oxygen and capacity limited thermal tolerance (OCLTT) as a framework integrating various drivers and linking organisational levels from ecosystem to organism, tissue, cell, and molecules. We suggest seven core objectives of a comprehensive research program comprising the interplay among physiological, ecological, and evolutionary approaches for both aquatic and terrestrial organisms. While studies of individual aspects are already underway in many laboratories worldwide, integration of these findings into conceptual frameworks is needed not only within one organism group such as animals but also across organism domains such as Archaea, Bacteria, and Eukarya. Indeed, development of unifying concepts is relevant for interpreting existing and future findings in a coherent way and for projecting the future ecological and evolutionary effects of climate change on functional biodiversity. We also suggest that OCLTT may in the end and from an evolutionary point of view, be able to explain the limited thermal tolerance of metazoans when compared to other organisms.