bluuebunny/crossref_metadata_2025 huggingface dataset:
Projecting into Space: International Student Projects
Authors: Leach Neil
Published: November 2014

As Guest‐Editor Neil Leach highlights, designing for Space vacillates between two distinct approaches, ‘the mercilessly functional or the indulgently fantastic’ with little middle ground. Here he features the work of students internationally that embody these two discrete strands, from RMIT University in Melbourne, California Polytechnic State University (Cal Poly), the University of California, Los Angeles (UCLA), University of Applied Arts Vienna, University of Southern California (USC), Dessau Institute of Architecture (DIA) in Germany, and the Sasakawa International Center for Space Architecture (SICSA) at the University of Houston.
Terrestrial Feedback: Reflections on the Space Industry
Authors: Leach Neil
Published: November 2014

Guest‐Editor Neil Leach contemplates the current status quo of space exploration and our attitudes towards it. Whereas in the 1960s the space industry was driven by the competitive enmity of the Cold War, how are our outlooks and initiatives calibrated now by earthbound considerations? How do approaches towards Space reflect those on Earth? Has a view from Space, for instance, enabled us to recognize the preciousness of our planet as it increasingly comes under fire? What opportunities does Space afford for technological transfer from the extraterrestrial to the terrestrial?
Graphite Oxide and Aromatic Amines: Size Matters
Authors: Spyrou Konstantinos , Calvaresi Matteo , Diamanti Evmorfia K. , Tsoufis Theodoros , Gournis Dimitrios , Rudolf Petra , Zerbetto Francesco
Published: November 2014

Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molecules prefer to covalently connect to the graphene oxide matrix via chemical grafting, while napthalene amine molecules bind with the graphene oxide surface through π–π interactions. The presence of intercalated aromatic molecules between the graphene oxide layers is demonstrated by X‐ray diffraction, while the type of interaction between graphene oxide and polycyclic organic molecules is elucidated by X‐ray photoelectron spectroscopy. Combined quantum mechanical and molecular mechanical calculations describe the intercalation mechanism and the aniline grafting, rationalizing the experimental data. The present work opens new perspectives for the interaction of various aromatic molecules with graphite oxide and the so‐called “intercalation chemistry”.
Copper‐Catalyzed Direct CH Arylation of Thieno[3,4‐c]pyrrole‐4,6‐dione (TPD): Toward Efficient and Low‐Cost Synthesis of π‐Functional Small Molecules
Authors: Song Yi‐Ting , Lin Po‐Han , Liu Ching‐Yuan
Published: November 2014

A series of thieno[3,4‐c]pyrrole‐4,6‐dione (TPD)‐based functional small molecules were efficiently synthesized through direct CH arylations using inexpensive copper salts. In this study, we examined all required reaction parameters including various copper complexes, ligands, bases, and (co)solvents. Under the optimum reaction conditions, the CH arylation proceeded smoothly and a variety of functional groups such as ester, nitrile, fluoride, chloride, triazene, and amine were tolerated. This method provides a step‐economical and relatively low‐cost synthetic alternative to presently used coupling reactions for the preparation of TPD‐containing π‐functional materials.

magnified image
A Flexible Porous Carbon Nanofibers‐Selenium Cathode with Superior Electrochemical Performance for Both Li‐Se and Na‐Se Batteries
Authors: Zeng Linchao , Zeng Wencong , Jiang Yu , Wei Xiang , Li Weihan , Yang Chenglong , Zhu Yanwu , Yu Yan
Published: November 2014

A flexible and free‐standing porous carbon nanofibers/selenium composite electrode (Se@PCNFs) is prepared by infiltrating Se into mesoporous carbon nanofibers (PCNFs). The porous carbon with optimized mesopores for accommodating Se can synergistically suppress the active material dissolution and provide mechanical stability needed for the film. The Se@PCNFs electrode exhibits exceptional electrochemical performance for both Li‐ion and Na‐ion storage. In the case of Li‐ion storage, it delivers a reversible capacity of 516 mAh g−1 after 900 cycles without any capacity loss at 0.5 A g−1. Se@PCNFs still delivers a reversible capacity of 306 mAh g−1 at 4 A g−1. While being used in Na‐Se batteries, the composite electrode maintains a reversible capacity of 520 mAh g−1 after 80 cycles at 0.05 A g−1 and a rate capability of 230 mAh g−1 at 1 A g−1. The high capacity, good cyclability, and rate capability are attributed to synergistic effects of the uniform distribution of Se in PCNFs and the 3D interconnected PCNFs framework, which could alleviate the shuttle reaction of polyselenides intermediates during cycling and maintain the perfect electrical conductivity throughout the electrode. By rational and delicate design, this type of self‐supported electrodes may hold great promise for the development of Li‐Se and Na‐Se batteries with high power and energy densities.
Partial pyruvate kinase deficiency aggravates the phenotypic expression of band 3 deficiency in a family with hereditary spherocytosis
Authors: van Zwieten Rob , van Oirschot Brigitte A. , Veldthuis Martijn , Dobbe Johannes G. , Streekstra Geert J. , van Solinge Wouter W. , Schutgens Roger E.G. , van Wijk Richard
Published: November 2014

In a family with mild dominant spherocytosis, affected members showed partial band 3 deficiency. The index patient showed more severe clinical symptoms than his relatives, and his red blood cells displayed concomitant low pyruvate kinase activity. We investigated the contribution of partial PK deficiency to the phenotypic expression of mutant band 3 in this family. Pyruvate kinase deficiency and band 3 deficiency were characterized by DNA analysis. Results of red cell osmotic fragility testing, the results of cell deformability obtained by the Automated Rheoscope and Cell Analyzer and the results obtained by Osmotic Gradient Ektacytometry, which is a combination of these tests, were related to the red cell ATP content. Spherocytosis in this family was due to a novel heterozygous mutation in SLC4A1, the gene for band 3. Reduced PK activity of the index patient was attributed to a novel mutation in PKLR inherited from his mother, who was without clinical symptoms. Partial PK deficiency was associated with decreased red cell ATP content and markedly increased osmotic fragility. This suggests an aggravating effect of low ATP levels on the phenotypic expression of band 3 deficiency. Am. J. Hematol. 90:E35–E39, 2015. © 2014 Wiley Periodicals, Inc.
Alu elements and the phylogeny of capuchin (Cebus and Sapajus) monkeys
Authors: Martins Antonio M.G. , Amorim Nadia , Carneiro Jeferson C. , de Mello Affonso Paulo Roberto Antunes , Sampaio Iracilda , Schneider Horacio
Published: November 2014

Three families of New World monkeys, the Pitheciidae, Atelidae, and Cebidae, are currently recognized. The monophyly of the Cebidae is supported unequivocally by the presence of ten unique Alu elements, which are absent from the other two families. In this paper, the five genomic regions containing these Alu elements were sequenced in specimens representing nine capuchin (Cebus, Sapajus) species in order to identify mutations that may help elucidate the taxonomy and phylogenetic relationships of the cebids. The results confirmed the presence of previously described Alu elements in the capuchins. An Alu insertion present in the Cebidae2 genomic region belonging to the AluSc subfamily was amplified and sequenced only in Sapajus. No amplified or unspecific product was obtained for all other species studied here. An AluSc insertion present in the CeSa1 region was found only in Cebus, Sapajus, and Saimiri. Cebidae4 was characterized by two insertions, an AluSz6 shared by all cebids, and a complete SINE (AluSx3) found only in the capuchins (Cebus and Sapajus). The genomic region Cebidae5 revealed two insertion events, one of the AluSx subfamily, which was shared by all cebids, and another (AluSc8), that was unique to Cebus, offering a straightforward criterion for the differentiation of the two genera, Cebus and Sapajus. The Cebidae6 region showed four distinct insertion events: a 52‐bp simple repeat ((TATG) n), two very ancient repeats (MIRc) and a TcMar‐Tigger shared by all New World monkeys studied so far, and an Alu insertion of the AluSx subfamily present exclusively in the cebids. The phylogenetic tree confirmed the division of the capuchins into two genera, Cebus and Sapajus, and suggested the southern species Sapajus nigritus robustus and S. cay as the earliest and second earliest offshoots in this genus, respectively. This supports a southern origin for the Sapajus radiation. Am. J. Primatol. 77:368–375, 2015. © 2014 Wiley Periodicals, Inc.
Size and placement of developing anterior teeth in immature Neanderthal mandibles from Dederiyeh Cave, Syria: Implications for emergence of the modern human chin
Authors: Fukase Hitoshi , Kondo Osamu , Ishida Hajime
Published: November 2014

Evolutionary and functional significance of the human chin has long been explored from various perspectives including masticatory biomechanics, speech, and anterior tooth size. Recent ontogenetic studies have indicated that the spatial position of internally forming anterior teeth partially constrains adult mandibular symphyseal morphology. The present study therefore preliminarily examined the size and placement of developing anterior teeth in immature Neanderthal mandibles of Dederiyeh 1 and 2, compared with similarly‐aged modern humans (N = 16) and chimpanzees (N = 7) whose incisors are comparatively small and large among extant hominids, respectively. The Dederiyeh 1 mandible is described as slightly presenting a mental trigone and attendant mental fossa, whereas Dederiyeh 2 completely lacks such chin‐associated configurations. Results showed that, despite symphyseal size being within the modern human range, both Dederiyeh mandibles accommodated overall larger anterior dentition and displayed a remarkably wide bicanine space compared to those of modern humans. Dederiyeh 2 had comparatively thicker deciduous incisor roots and more enlarged permanent incisor crypts than Dederiyeh 1, but both Dederiyeh individuals exhibited a total dental size mostly intermediate between modern humans and chimpanzees. These findings potentially imply that the large deciduous/permanent incisors collectively distended the labial alveolar bone, obscuring an incipient mental trigone. It is therefore hypothesized that the appearance of chin‐associated features, particularly of the mental trigone and fossa, can be accounted for partly by developmental relationships between the sizes of the available mandibular space and anterior teeth. This hypothesis must be, however, further addressed with more referential samples in future studies. Am J Phys Anthropol 156:482–488, 2015. © 2014 Wiley Periodicals, Inc.
Endoscopic endonasal resection of respiratory epithelial adenomatoid hamartomas of the sinonasal tract
Authors: Bignami Maurizio , Volpi Luca , Karligkiotis Apostolos , De Bernardi Francesca , Pistochini Andrea , AlQahtani AbdulAziz , Meloni Francesco , Verillaud Benjamin , Herman Philippe , Castelnuovo Paolo
Published: November 2014

Background

Respiratory epithelial adenomatoid hamartomas (REAHs) are rare benign tumors and may manifest as either isolated lesions or in association with sinonasal polyposis. The aim of this study is to report our experience in the management of patients with REAH and to analyze the long‐term results of the endoscopic endonasal approach.

Methods

A retrospective analysis of a database dedicated to patients with REAH treated between May 2003 and December 2012 was performed. Clinical presentation, demographic, histologic and radiographic features, operative findings, and follow‐up data were examined.

Results

Twenty‐seven patients with REAH, 14 males and 13 females, with a mean age of 51 years, underwent endoscopic sinus surgery (ESS). The most frequent reported symptoms were nasal obstruction (80%), headache (12%), mucous rhinorrhea (20%), and hyposmia (40%). Seventeen cases (first group) were present as isolated masses, 10 cases (second group) were associated with nasal polyposis. The first group with a preoperative diagnosis of REAH was submitted to a more aggressive resection with subperiosteal dissection and drilling of the underlying bone. The patients in the second group, because of the unrevealed diagnosis of REAH and due to the presence of nasal polyposis, underwent standard ESS. No evidence of recurrence in either of the subgroups after a mean follow‐up of 61.2 months.

Conclusion

REAH is a benign well‐defined pathological entity but is still unfamiliar. REAH should be kept in mind as a differential diagnosis from more aggressive lesions to avoid unnecessary surgical procedure. A complete but conservative endoscopic resection appears to be curative.
Argentophilic Interactions
Authors: Schmidbaur Hubert , Schier Annette
Published: November 2014

The decade 1990–2000 saw a growing interest in aurophilic interactions in gold chemistry. These interactions were found to influence significantly a variety of structural and other physical characteristics of gold(I) compounds. The attention paid to this unusual and counterintuitive type of intra‐ and intermolecular bonding between seemingly closed‐shell metal centers has rapidly been extended to also include silver chemistry. Hundreds of experimental and computational studies have since been dedicated to the argentophilicity phenomenon. The results of this development are reviewed herein focusing on molecular systems where two or more silver(I) centers are in close contact leading to specific structural characteristics and a variety of novel physical properties. These include strongly modified ligand‐to‐metal charge‐transfer processes observed in absorption and emission spectroscopy, but also colossal positive and negative thermal expansion on the one hand and unprecedented negative linear compressibility of crystal parameters on the other.
Ambient Stable Zwitterionic Perylene Bisimide‐Centered Radical
Authors: Schmidt David , Bialas David , Würthner Frank
Published: November 2014

The unexpected introduction of a cationic imidazolium substituent in the 2‐position of a tetrachloro‐substituted perylene‐3,4:9,10‐tetracarboxylic acid bisimide (PBI) by the reaction of PBI‐Cl4 1 with the N‐heterocyclic carbene 1,3‐di‐iso‐propyl‐imidazolin‐2‐ylidene (iPr2Im 2) enables the isolation of an ambient stable zwitterionic radical. The remarkable stability of this unprecedented PBI‐centered radical facilitates the complete characterization by several spectroscopic methods as well as single crystal structure analysis. Redox studies revealed that iPr2Im‐PBI‐Cl4 4 can be transferred reversibly to the corresponding anion and cation, respectively, even on a preparative scale.
The Expression and Role of MEKK3 in Renal Clear Cell Carcinoma
Authors: Lu Hongsheng , Cao Xuequan , Chen Qi , Chen Lanxi , Chen Lili , Gan Meifu
Published: November 2014

To explore the relationship between Mitogen‐activated protein kinase/extracellular signal‐regulated kinase kinase kinase 3(MEKK3) and cell apoptosis, clinicopathology, and prognosis, we characterize the expression of MEKK3, survivin and stat3 in renal clear cell carcinoma (RCCC). The expressions were measured by RT‐PCR and Western blot from 15 cases of RCCC and 15 cases of control group (CG). Protein expression was detected by tissue microarray and immunochemistry in 98 cases of RCCC, 28 cases of CG. Expression patterns were analyzed for their association with pathological factors, correlation and prognosis in RCCC. Expression of MEKK3, survivin and stat3 mRNA was significantly higher in RCCC than in CG (P < 0.01). MEKK3, survivin and stat3 expression differed significantly between pathological grade (P < 0.05) and clinical stage (P < 0.05). MEKK3 expression was positively correlated with survivin and stat3 (P < 0.01). Furthermore, we investigated the role of MEKK3 in RCCC using the technique of RNA silencing via small interfering (siRNA) in ACHN cells. The results indicated that the targeted depletion of MEKK3 caused a dramatic massive apoptotic cell death. Kaplan–Meier survival analysis showed that MEKK3 and survivin expression, pathological grade, and clinical stage reduced cumulative survival. Cox multivariate regression analysis showed that MEKK3, survivin, and clinical staging were independent prognostic factors in renal cancer (P < 0.05). MEKK3 can be used as an important marker of prognostic evaluation in RCCC. The mechanism may be closely related to cell apoptosis. Targeted therapy of MEKK3 may provide a new strategy for treatment of chemotherapeutic‐resistant tumors. Anat Rec, 298:727–734, 2015. © 2014 Wiley Periodicals, Inc.
Efficient Synthesis of Aza‐triquinacene Derivatives via Cycloaddition of 2,6‐Diazasemibullvalenes with Nitroso Compounds
Authors: Zhan Ming , Zhang Shaoguang , Huang Zhe , Xi Zhenfeng
Published: November 2014

The reaction between 2,6‐diazasemibullvalenes and nitroso compounds was investigated. Aza‐triquinacene derivatives of interesting structural and synthetic chemistry were generated highly selectively in good to excellent isolated yields. This reaction, which was rarely found between common aziridine derivatives and nitroso compounds, could be attributed to the rigid polycyclic ring system and the substitution patterns of 2,6‐diazasemibullvalenes. Δ1‐Bipyrroline derivatives were formed in excellent yields when these aza‐triquinacene derivatives were treated with SmI2.
ROGA – A New Method for Risk‐Based Hazard Analysis: Part 1 – Deductive Hazard Analysis and Risk‐Based Assessment by Using a Risk Graph
Authors: Bock Franz‐Josef , Haferkamp Klaus
Published: November 2014

This paper proposes a new method, risk‐oriented hazard analysis (ROGA), for carrying out the risk‐based hazard analysis of chemical plants. The aim of ROGA method is to determine the status of a plant's safety technology by determining the risk that arises as a result of a source of hazard taking effect and by evaluating all measures taken to control this risk. The contribution consists of two parts. In this first part, the deductive hazard analysis and its extension by a semi‐quantitative risk assessment associated with sources of hazards is explained with the help of a risk graph.
ROGA – A New Method for Risk‐Based Hazard Analysis: Part 2 – Semi‐Quantitative Assessment and Implementation of the Hazard Analysis
Authors: Bock Franz‐Josef , Haferkamp Klaus
Published: November 2014

In the first part of this article, the deductive hazard analysis and its extension by a semi‐quantitative risk assessment of sources of hazards were presented. This was done by using a calibrated risk graph. In this second part now, the semi‐quantitative assessment of the dependability of safety measures is pointed out. The safety check is carried out by comparing the risk classes with dependability classes which are applied to both operational and technical measures. Now this paper describes the requirements for ROGA arising from the stipulations of the international standards like IEC 61508/11.
A Critique of Recent Semi‐Classical Spin‐Half Quantum Plasma Theories
Authors: Krishnaswami G. S. , Nityananda R. , Sen A. , Thyagaraja A.
Published: November 2014

Certain recent semi‐classical theories of spin‐half quantum plasmas are examined with regard to their internal consistency, physical applicability and relevance to fusion, astrophysical and condensed matter plasmas. It is shown that the derivations and some of the results obtained in these theories are internally inconsistent and contradict well‐established principles of quantum and statistical mechanics, especially in their treatment of fermions and spin. Claims of large semi‐classical effects of spin magnetic moments that could dominate the plasma dynamics are found to be invalid both for single‐particles and collectively. Larmor moments dominate at high temperature while spin moments cancel due to Pauli blocking at low temperatures. Explicit numerical estimates from a variety of plasmas are provided to demonstrate that spin effects are indeed much smaller than many neglected classical effects. The analysis presented suggests that the aforementioned ‘Spin Quantum Hydrodynamic’ theories are not relevant to conventional laboratory or astrophysical plasmas. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Carbon isotope ratios of nandrolone, boldenone, and testosterone preparations seized in Norway compared to those of endogenously produced steroids in a Nordic reference population
Authors: Hullstein Ingunn , Sagredo Carlos , Hemmersbach Peter
Published: November 2014

Determining the origin of anabolic androgenic steroids (AAS) that also are produced endogenously in the human body is a major issue in doping control. In some cases, the presence of nandrolone and boldenone metabolites might result from endogenous production. The GC‐C‐IRMS technique (gas chromatography‐combustion‐isotope ratio mass spectrometry) enables the carbon isotopic ratio (CIR) to be measured to determine the origin of these metabolites. The aim of this study was to use GC‐C‐IRMS to determine the δ13CVPDBvalues of seized boldenone and nandrolone preparations to decide if the steroids themselves were depleted in13C, compared to what is normally seen in endogenously produced steroids. In addition, several testosterone preparations were analyzed. A total of 69 seized preparations were analyzed. The nandrolone preparations showed δ13CVPDBvalues in the range of ‐31.5 ‰ to ‐26.7 ‰. The boldenone preparations showed δ13CVPDBvalues in the range of ‐32.0 ‰ to ‐27.8 ‰, and for comparison the testosterone preparations showed δ13CVPDBvalues of ‐31.0 ‰ to ‐24.2 ‰. The results showed that the values measured in the nandrolone and boldenone preparations were in the same range as those measured in the testosterone preparations. The study also included measurements of CIR of endogenously produced steroids in a Norwegian/Danish reference population. The δ13CVPDBvalues measured for the endogenous steroids in this population were in the range of ‐21.7 to ‐26.8. In general, most of the preparations investigated in this study show13C‐depleted delta values compared to endogenously produced steroids reflecting a northern European diet. Copyright © 2014 John Wiley & Sons, Ltd.
Statistical significance of hair analysis of clenbuterol to discriminate therapeutic use from contamination
Authors: Krumbholz Aniko , Anielski Patricia , Gfrerer Lena , Graw Matthias , Geyer Hans , Schänzer Wilhelm , Dvorak Jiri , Thieme Detlef
Published: November 2014

Clenbuterol is a well‐established β2‐agonist, which is prohibited in sports and strictly regulated for use in the livestock industry. During the last few years clenbuterol‐positive results in doping controls and in samples from residents or travellers from a high‐risk country were suspected to be related the illegal use of clenbuterol for fattening. A sensitive liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) method was developed to detect low clenbuterol residues in hair with a detection limit of 0.02 pg/mg. A sub‐therapeutic application study and a field study with volunteers, who have a high risk of contamination, were performed. For the application study, a total dosage of 30 µg clenbuterol was applied to 20 healthy volunteers on 5 subsequent days. One month after the beginning of the application, clenbuterol was detected in the proximal hair segment (0‐1 cm) in concentrations between 0.43 and 4.76 pg/mg. For the second part, samples of 66 Mexican soccer players were analyzed. In 89% of these volunteers, clenbuterol was detectable in their hair at concentrations between 0.02 and 1.90 pg/mg. A comparison of both parts showed no statistical difference between sub‐therapeutic application and contamination. In contrast, discrimination to a typical abuse of clenbuterol is apparently possible. Due to these findings results of real doping control samples can be evaluated. Copyright © 2014 John Wiley & Sons, Ltd.
Hox and ParaHox genes: A review on molluscs
Authors: Biscotti Maria Assunta , Canapa Adriana , Forconi Mariko , Barucca Marco
Published: November 2014

Hox and ParaHox genes are involved in patterning the anterior‐posterior body axis in metazoans during embryo development. Body plan evolution and diversification are affected by variations in the number and sequence of Hox and ParaHox genes, as well as by their expression patterns. For this reason Hox and ParaHox gene investigation in the phylum Mollusca is of great interest, as this is one of the most important taxa of protostomes, characterized by a high morphological diversity. The comparison of the works reviewed here indicates that species of molluscs, belonging to different classes, share a similar composition of Hox and ParaHox genes. Therefore evidence suggests that the wide morphological diversity of this taxon could be ascribed to differences in Hox gene interactions and expressions and changes in the Hox downstream genes rather than to Hox cluster composition. Moreover the data available on Hox and ParaHox genes in molluscs compared with those of other Lophotrochozoa shed light on the complex and controversial evolutionary histories that these genes have undergone within protostomes. genesis 52:935–945, 2014. © 2014 Wiley Periodicals, Inc.
Genomic organization of Hox and ParaHox clusters in the echinoderm, Acanthaster planci
Authors: Baughman Kenneth W. , McDougall Carmel , Cummins Scott F. , Hall Mike , Degnan Bernard M. , Satoh Nori , Shoguchi Eiichi
Published: November 2014

The organization of echinoderm Hox clusters is of interest due to the role that Hox genes play in deuterostome development and body plan organization, and the unique gene order of the Hox complex in the sea urchin Strongylocentrotus purpuratus, which has been linked to the unique development of the axial region. Here, it has been reported that the Hox and ParaHox clusters of Acanthaster planci, a corallivorous starfish found in the Pacific and Indian oceans, generally resembles the chordate and hemichordate clusters. The A. planci Hox cluster shared with sea urchins the loss of one of the medial Hox genes, even‐skipped (Evx) at the anterior of the cluster, as well as organization of the posterior Hox genes. genesis 52:952–958, 2014. © 2014 Wiley Periodicals, Inc.
Possible Roles of the Spatial Distribution of Organic Guest Species in Mesoporous Silicas to Control the Properties of the Hybrids
Authors: Ogawa Makoto , Saito Kanji , Sohmiya Minoru
Published: November 2014

Mesoporous silicas are promising materials for the construction of host–guest hybrids by the accommodation of functional unit/guest species into the mesopore, and moreover, by hierarchical assembly with controlled location, density, and orientation. Precisely designed structures open up the versatile functions of mesoporous silicas and their host–guest systems. In this microreview, the spatial distribution (location, density, and orientation) of the organic functional units/guest species in mesoporous silicas (mainly one‐dimensional cylindrical) is discussed to highlight the present status of the host–guest chemistry of mesoporous silicas.
Oxidation of Alkylbenzenes with Cerium Complexes Containing a Tripodal Oxygen Ligand
Authors: Yi Xiao‐Yi , Wang Guo‐Cang , Ip Ho‐Fai , Wong Wai‐Yeung , Chen Lizhuang , Sung Herman H. ‐Y. , Williams Ian D. , Leung Wa‐Hung
Published: November 2014

The treatment of [Ce(LOEt)2(NO3)2] (LOEt– = [Co(η5‐C5H5){P(O)(OEt)2}3]–) with KMnO4 in water afforded a diamagnetic purple solid 1, which is tentatively formulated as a CeIV permanganate complex, “[Ce(LOEt)2(MnO4)2]”. The ZrIV analogue, [Zr(LOEt)2(MnO4)2] (2), has been prepared similarly from [Zr(LOEt)2(NO3)2] and KMnO4. The recrystallization of 1 from CH2Cl2/hexanes at –18 °C led to the isolation of dinuclear [(CeLOEt)2(μ‐LOEt′)2][MnO4]2 (3), which contains the dianionic tripodal ligand [LOEt′]2– ([(η5‐C5H5)Co{P(O)(OEt)2}2{P(O)2(OEt)}]2–). The reactions of 1 with K[ReO4] and [NH4][OsO3N] afforded the heterodimetallic complexes [Ce(LOEt)2(ReO4)2] (4) and [Ce(LOEt)2(NOsO3)2] (5), respectively. The crystal structures of 3 and 5 have been determined. Freshly prepared 1 can oxidize alkylbenzenes such as toluene, ethylbenzene, and cumene at room temperature to give the corresponding ketone and/or alcohol products. Ce–LOEt complexes are efficient promoters of the aerobic oxidation of alkylbenzenes by a radical mechanism. For example, cumene in the presence of [Ce(LOEt)2(H2O)2]Cl (1 mM) in air at 100 °C for 10 h afforded a ca. 6:1 mixture of 2‐phenyl‐2‐propanol and acetophenone with a total turnover number of 6810.
Systematic Variation of Cyanobuta‐1,3‐dienes and Expanded Tetracyanoquinodimethane Analogues as Electron Acceptors in Photoactive, Rigid Porphyrin Conjugates
Authors: Urner Lorenz M. , Sekita Michael , Trapp Nils , Schweizer W. Bernd , Wörle Michael , Gisselbrecht Jean‐Paul , Boudon Corinne , Guldi Dirk M. , Diederich François
Published: November 2014

We report on a homologous series of nine electron donor–acceptor systems featuring push–pull chromophores as electron acceptors, which are accessible by a cycloaddition‐retroelectrocyclization (CA‐RE) reaction. The conjugates comprise a ZnII porphyrin as electron donor, which is connected through either a rigid phenylene‐ethynylene‐phenylene (PEP)‐bicyclo[2.2.2]octane or a PEP‐trans‐decahydroquinoline spacer to different anilino‐substituted multicyanobutadienes or extended tetracyanoquinodimethane analogues with first reduction potentials ranging from –1.78 to –0.58 V vs. Fc+/Fc. Characterization of the conjugates includes X‐ray crystallography, electrochemistry, DFT calculations, and fluorescence spectroscopy. The extent of ZnII porphyrin fluorescence quenching correlates with the strength of the electron acceptor. Overall, we demonstrate the synthetic feasibility of rationally modulating the acceptor strength by means of the CA‐RE reaction in geometrically well‐defined electron donor–acceptor conjugates.
Environmental Impacts of Shale Gas in the UK: Current Situation and Future Scenarios
Authors: Cooper Jasmin , Stamford Laurence , Azapagic Adisa
Published: November 2014

This paper presents life cycle environmental impacts of UK shale gas used for electricity generation, in comparison with other fossil, nuclear and renewable options. Per kWh of electricity generated, shale gas has higher environmental impacts than the other options, except for coal. Thus, if it were to replace coal, most impacts would be reduced, including the global warming potential (GWP; by 2.3 times). However, if it were to compete with nuclear or some renewables most impacts would rise, with the GWP increasing by 5–123 times. Within a future UK electricity mix up to 2030, shale gas would make little difference to the environmental impacts of electricity generation, including the GWP, even for the most optimistic assumptions for its domestic production. This suggests that, in the medium term, shale gas cannot help towards meeting UK climate change targets and that certain renewables and nuclear power should be prioritized instead.
Dissolved trace metal speciation in estuarine and coastal waters: Comparison of WHAM/Model VII predictions with analytical results
Authors: Stockdale Anthony , Tipping Edward , Lofts Stephen
Published: November 2014

The authors apply the chemical speciation model WHAM/Model VII to investigate the distribution of metal species of Fe(III) and the divalent cations of Ni, Cu, Zn, Cd, Hg, and Pb, in the water column of estuaries and coastal areas. The authors compare, for the same locations, measured and modeled free ion and organically bound metal concentrations. The modeled free ion calculations show varying levels of agreement with experimental measurements. Where only natural organic matter is considered as the organic ligand, for Ni, Cd, and Pb, agreement within 1 order of magnitude is found in 122 of 128 comparisons. For Fe and Zn comparisons 12 of 34 (Fe) and 10 of 18 (Zn) agree to within 1 order of magnitude, the remaining modeled values being over 1 order of magnitude higher than measurements. Copper measurements agree within 1 order of magnitude of modeled values in 314 of 533 (59%) cases and are more than 1 order of magnitude lower than modeled values in 202 cases. There is a general tendency for agreement between modeled and measured values to improve with increasing total metal concentrations. There are substantial variations among different analysis techniques but no systematic bias from the model is observed across techniques. It would be beneficial to cross-validate the different analytical methods, in combination with further modeling. The authors also assessed the effect of including an anthropogenic organic ligand (ethylenediamine tetraacetic acid (EDTA)) in the modeling, given its known presence in some coastal environments. Except for Cd, all metals were sensitive to the presence of EDTA, even at a low concentration of 50 nM. Environ Toxicol Chem 2015;34:53–63. © 2014 SETAC. The copyright statement for this article was changed in September 2016, after its original publication.
White matter abnormalities associated with military PTSD in the context of blast TBI
Authors: Davenport Nicholas D. , Lim Kelvin O. , Sponheim Scott R.
Published: November 2014

Mild traumatic brain injury (mTBI) and post‐traumatic stress disorder (PTSD) are common among recent military veterans and involve substantial symptom overlap, making clinical distinction and effective intervention difficult. Emerging evidence of cerebral white matter abnormalities associated with mTBI may provide a biological measure to inform diagnosis and treatment, but the potentially confounding effects between PTSD and mTBI have largely gone unexamined. We collected diffusion imaging data from 133 recently‐deployed American service members who developed PTSD and/or sustained mTBI, or had neither condition. Effects of PTSD and mTBI on traditional tensor‐based measures of cerebral white matter integrity (fractional anisotropy [FA] and mean diffusivity [MD]) were compared in anatomical regions of interest and individual voxels throughout the brain. Generalized FA (GFA), which allows for multiple fiber orientations per voxel, was also included to improve sensitivity in white matter areas containing crossing or diverging axon bundles. PTSD was consistently associated with high GFA in select brain regions, greater likelihood of regions and voxels with abnormally low MD, and a greater number of voxels with abnormally high FA, while mTBI was associated with fewer high MD regions. Overall, PTSD was associated with more restricted diffusion (low MD) and greater anisotropy (high GFA) in regions of crossing/diverging fibers poorly characterized by a single tensor (FA), suggesting that interstitial fibers may be involved. Contrary to earlier results in a sample without PTSD, mTBI was not associated with anisotropy abnormalities, perhaps indicating the cooccurrence of PTSD and mTBI requires special consideration with regard to structural brain connectivity. Hum Brain Mapp 36:1053–1064, 2015. © 2014 Wiley Periodicals, Inc.
Accuracy of ultrasound for predicting pathologic response during neoadjuvant therapy for breast cancer
Authors: Marinovich Michael Luke , Houssami Nehmat , Macaskill Petra , von Minckwitz Gunter , Blohmer Jens‐Uwe , Irwig Les
Published: November 2014

Early assessment of response to neoadjuvant chemotherapy (NAC) for breast cancer allows therapy to be tailored; however, optimal response assessment methods have not been established. We estimated the accuracy of ultrasound (US) to predict pathologic complete response (pCR) using common response criteria and pCR definitions, and estimated incremental accuracy over known prognostic variables. Participants undergoing US after two cycles in the GeparTrio trial randomised to no change in NAC were eligible. US response by World Health Organisation (WHO) criteria (1D or 2D) and Response Evaluation Criteria In Solid Tumours (RECIST) was assessed. Four pCR definitions were applied. Sensitivity (correct prediction of pCR), specificity (correct prediction of no‐pCR) and diagnostic odds ratios (DORs) were calculated. Areas under the curve (AUCs) were derived from logistic regression including patient variables with and without US. In 832 patients, DORs decreased as pCR definitions became less stringent (p = 0.01). For WHO‐2D, DORs were as follows: 4.07 (ypT0,ypN0), 3.75 (ypT0/is,ypN0), 3.14 (ypT0/is,ypN+/−) and 2.65 (ypT0/is/1a,ypN+/−). DORs did not differ between US criteria (p = 0.60). High sensitivity and lower specificity were found for WHO‐2D and RECIST; WHO‐1D was highly specific with low sensitivity. Sensitivity was highest for WHO‐2D predicting ypT0,ypN0 (sensitivity = 81.7%, specificity = 47.6% vs. 42.3% and 80.4% for WHO‐1D). Adding US to models including patient variables (age, T‐stage, histology and subtype) improved AUCs for predicting pCR by 2–3%. In conclusion, US accuracy is highest for predicting ypT0,ypN0, shown to be most prognostic of long‐term survival. WHO‐2D and RECIST maximise sensitivity; WHO‐1D maximises specificity. US modestly improves the prediction of pCR by patient characteristics.
Human papillomavirus type 197 is commonly present in skin tumors
Authors: Arroyo Mühr L. Sara , Hultin Emilie , Bzhalava Davit , Eklund Carina , Lagheden Camilla , Ekström Johanna , Johansson Hanna , Forslund Ola , Dillner Joakim
Published: November 2014

Non‐melanoma skin cancers commonly contain Human Papillomavirus (HPV), but the types found have varied depending on the polymerase chain reaction (PCR) primer systems used. Whole genome amplified DNA (not amplified by any specific PCR primers) from 91 skin lesions [41 squamous cell skin carcinomas (SCCs), 8 keratoacanthomas, 22 actinic keratoses, 3 basal cell carcinomas and 17 SCCs in situ] were sequenced. All samples were sequenced both at 160 Mb and 1.8 Gb sequencing depth per sample. The sequences from 10 different HPVs in 47/91 specimens were found. Sequences represented four established HPV types (HPV types 16, 22, 120, 124), two previously known putative types (present in GenBank) and four previously unknown HPV sequences (new putative types). The most commonly detected virus was cloned, sequenced and designated as HPV197. Type‐specific real‐time PCR detected HPV197 in 34/91 specimens. For comparison, a pool of the same samples after general primer PCR amplification was also sequenced. This revealed 40 different HPVs, but only two HPV types were detected both with sequencing without prior PCR and with sequencing PCR amplicons, suggesting that sequencing without prior PCR gives a more unbiased representation of the HPVs present. In summary, it was found that HPV can be sequenced from most skin disease specimens and HPV197 appeared to be the most commonly present virus.
Inhibitors of BCR signalling interrupt the survival signal mediated by the micro‐environment in mantle cell lymphoma
Authors: Bernard Sophie , Danglade Damien , Gardano Laura , Laguillier Christelle , Lazarian Gregory , Roger Claudine , Thieblemont Catherine , Marzec Jacek , Gribben John , Cymbalista Florence , Varin‐Blank Nadine , Ledoux Dominique , Baran‐Marszak Fanny
Published: November 2014

Several studies provide evidences for mantle cell lymphoma (MCL) cell survival relying on B‐cell receptor (BCR)‐mediated signalling pathways, whereas the nature of this activation is unknown. Significant progress in MCL treatment is achieved through therapies targeting BCR‐associated kinases, i.e., Ibrutinib and Fostamatinib, inhibitors of BTK and SYK, respectively. Our study addresses survival signals emanating from the BCR or the tumour environment and how inhibiting BCR signalling effectors might impact these survival signals. We found that BTK was constitutively activated and that SYK phosphorylation was highly increased and sustained upon BCR activation of primary MCL cells. Moreover, MCL cells from leukaemic patients secreted high amount of IL‐1β, IL‐6, IL‐8 and CCL5. Activation of the BCR induced (i) cell survival, (ii) STAT3 activation and (iii) increased autocrine secretion of IL‐1β, IL‐6, IL‐8, CCL5, IL‐10, TNFα and VEGF. Specific inhibition of BTK by Ibrutinib or SYK by Fostamatinib (R406) reversed these protective effects and decreased both basal and BCR‐induced autocrine cytokine secretions associated with STAT3 phosphorylation. Interestingly, targeting BTK and SYK prevented and inhibited BCR‐induced MCL cell adhesion to human bone marrow stromal cells (HMSCs) in short‐ and long‐term co‐culture. We demonstrated that BCR‐induced survival relies on autocrine secretion of IL‐1β, TNFα and CCL5 that might facilitate adhesion of MCL cells to HMSC. Treatment with Ibrutinib or Fostamatinib blocked the chemotactic signal thus increasing apoptosis.
Fabrication of polyHEMA grids by micromolding in capillaries for cell patterning and single‐cell arrays
Authors: Ye Fang , Ma Binghe , Gao Jie , Xie Li , Wei Chen , Jiang Jin
Published: November 2014

Control of cell adhesion and growth by microfabrication technology and surface chemistry is important in an increasing number of applications in biotechnology and medicine. In this study, we developed a method to fabricate (2‐hydroxyethyl methacrylate) (polyHEMA) grids on glass by micromolding in capillaries (MIMIC). As a non‐fouling biomaterial, polyHEMA was used to inhibit the nonspecific bonding of cells, whereas the glass surface provided a cell adhesive background. The polyHEMA chemical barrier was directly obtained using MIMIC without surface modification, and the microchannel networks used for capillarity were easily achieved by reversibly bonding the polydimethylsiloxane (PDMS)mold and the glass. After fabrication of the polyHEMA micropattern, individual cytophilic microwells surrounded by cytophobic sidewalls were presented on the glass surface. The polyHEMA micropattern proved effective in controlling the shape and spreading of cells, and square‐shaped mouse osteoblast MC3T3‐E1 cells were obtained in microwell arrays after incubation for 3 days. Moreover, the widths of the microwells in this micropattern were optimized for use as single‐cell arrays. The proposed method could be a convenient tool in the field of drug screening, stem cell research, and tissue engineering. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 103B: 1375–1380, 2015.
Tetracycline tethered to titanium inhibits colonization by Gram‐negative bacteria
Authors: Davidson Helen , Poon Martin , Saunders Ray , Shapiro Irving M. , Hickok Noreen J. , Adams Christopher S.
Published: November 2014

As peri‐prosthetic infection is one of the most devastating complications associated with implant placement, we have reasoned that such infection can be largely subverted by development of antibacterial implants. Our previous work demonstrated that covalent coupling of vancomycin to titanium alloy prevented colonization by the Gram‐positive pathogens, Staphylococcus aureus and Staphylococcus epidermidis. Some orthopedic devices, including permanent prosthesis anchors, and most dental implants are transcutaneous or transmucosal and can be prone to colonization by Gram‐negative pathogens. We report here the successful covalent coupling of the broad‐spectrum antibiotic, tetracycline (TET), to titanium surfaces (Ti‐TET) to retard Gram‐negative colonization. Synthetic progress was followed by changes in water contact angle, while the presence of TET was confirmed by immunofluorescence. Ti‐TET actively prevented colonization in the presence of bathing Escherichia coli, both by fluorescence microscopy and direct counting. Finally, the Ti‐TET surface supported osteoblastic cell adhesion and proliferation over a 72‐h period. Thus, this new surface offers a powerful means to protect transcutaneous implants from adhesion of Gram‐negative pathogens, decreasing the need for replacement of this hardware. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 103B: 1381–1389, 2015.
The attraction of gambling
Authors: Rachlin Howard , Safin Vasiliy , Arfer Kodi B. , Yen Ming
Published: November 2014

If a repeated gamble is subjectively structured into units each consisting of a string of consecutive losses followed by a single win, longer strings will necessarily be less valuable. Longer, less valuable strings will be discounted by delay more than will shorter, more valuable strings. This implies that the whole gamble's expected, delay‐discounted value will increase as delay discounting increases. With this restructuring, even games of (objectively) negative expected value, such as those at casinos, may be subjectively positive. The steeper the delay discounting, the greater the subjective value of the gamble (over normal ranges of discounting steepness). Frequent gamblers, who value gambles highly, would thus be expected to discount delayed rewards more steeply than would nongamblers.
Minimum Vertex Degree Threshold for ‐tiling*
Authors: Han Jie , Zhao Yi
Published: November 2014

We prove that the vertex degree threshold for tiling (the 3‐uniform hypergraph with four vertices and two triples) in a 3‐uniform hypergraph on vertices is , where if and otherwise. This result is best possible, and is one of the first results on vertex degree conditions for hypergraph tiling.
On Sheehan's Conjecture for Graphs with Symmetry
Authors: Šajna Mateja , Wagner Andrew
Published: November 2014

Sheehan's Conjecture states that every hamiltonian 4‐regular graph possesses a second Hamilton cycle. In this article, we verify Sheehan's Conjecture for 4‐regular graphs of order n whose automorphism group has size at least if either for all , or for and m is either an odd prime or a power of 2. We also give lower bounds on the size of the automorphism group and degree of a regular hamiltonian graph that guarantee existence of a second Hamilton cycle.
Hydrogen sulfide functions as a neuromodulator to regulate striatal neurotransmission in a mouse model of Parkinson's disease
Authors: Wang Min , Zhu Jun , Pan Yang , Dong Jingde , Zhang Lili , Zhang Xiangrong , Zhang Li
Published: November 2014

Hydrogen sulfide (H2S), a novel endogenous gasotransmitter, has been considered a neuromodulator to enhance hippocampal long‐term potentiation and exerts neuroprotective effects against neurotoxin‐induced neurodegeneration in rodent models of Parkinson's disease (PD). However, whether H2S can function as a neuromodulator to regulate the levels of nigrostriatal neurotransmitters and then impact the vulnerability of dopaminergic (DA) neurons in response to neurotoxins remains unknown. For this study, we prepared a 1‐methyl‐4‐phenyl‐1,2,3,6‐tetrahydropyridine plus probenecid (MPTP/p)‐induced mouse subacute model of PD to explore the modulatory effect of H2S on monoamine and amino acid neurotransmitters in the striatum of MPTP‐treated mice. This study shows that NaHS (an H2S donor, 5.6 mg/kg/day, i.p.) administration improves the survival rate and significantly ameliorates the weight loss of MPTP‐treated mice. NaHS treatment attenuated MPTP‐induced neuronal damage, restored the diminution of DA neurons, and suppressed the overactivation of astrocytes in the mouse striatum. Additionally, NaHS upregulated striatal serotonin levels and modulated the balance of excitatory glutamate and the inhibitory γ‐aminobutyric acid system in response to MPTP challenge. The current study indicates that H2S may function as an effective neuromodulator to regulate striatal neurotransmission and provides insight into the potential of H2S for PD therapy. © 2014 Wiley Periodicals, Inc.