bluuebunny/crossref_metadata_2025 huggingface dataset:
Comparison of moderate to severe systemic reactions with honeybee and wasp in children
Authors: Karagol Hacer Ilbilge Ertoy , Bakirtas Arzu , Yilmaz Ozlem , Topal Erdem , Arga Mustafa , Demirsoy Mehmet Sadık , Turktas Ipek
Published: April 2014

Background

The effect of the type of Hymenoptera on the severity of systemic reactions (SRs) is a controversial issue. The aim of the present study was to evaluate demographic, clinical, diagnostic, and therapeutic features of moderate‐to‐severe SRs in children with venom hypersensitivity and to compare the role of the honeybee and wasp stings in these reactions.

Methods

Data on children with moderate‐to‐severe SRs after a Hymenoptera sting were retrospectively collected for a 17‐year period.

Results

A total of 55 children with moderate‐to‐severe SRs (wasp: 44, honeybee: 11) to venom stings were included in the study. In the honeybee group, comorbid allergic rhinitis and any type of atopic disease was more frequent compared to the wasp group (p = 0.009 and p = 0.01, respectively). In 50.9% of the children, family history of SR to the same venom type was higher in the honeybee group (p = 0.02). Dyspnea was more frequent in the wasp, and cyanosis was more frequent in the honeybee compared to each other (p = 0.02 and p < 0.001, respectively). Prick tests results were significantly different between the groups (p = 0.038). There was no difference between honeybee and wasp in moderate‐to‐severe SR groups in terms of seasonal tendency, age at admission, age at first SR, gender, previous history of SR, sting localization, latency, and affected organ systems (p > 0.05 for each).

Conclusion

Moderate‐to‐severe SRs with honeybee and wasp venoms in children may differ in the severity of respiratory symptoms/signs at presentation, in addition to comorbidity of atopic diseases and family history of the SRs.
Differential loss of KIR4.1 immunoreactivity in multiple sclerosis lesions
Authors: Schirmer Lucas , Srivastava Rajneesh , Kalluri Sudhakar Reddy , Böttinger Susanne , Herwerth Marina , Carassiti Daniele , Srivastava Barkha , Gempt Jens , Schlegel Jürgen , Kuhlmann Tanja , Korn Thomas , Reynolds Richard , Hemmer Bernhard
Published: April 2014

Objective

Serum antibodies against the glial potassium channel KIR4.1 are found in a subpopulation of multiple sclerosis (MS) patients. Little is known about the expression of KIR4.1 in human normal brain tissue and in MS lesions.

Methods

We analyzed the expression pattern of KIR4.1 in normal brain tissue and MS lesions of the subcortical white matter by immunohistochemistry. Markers of related glial proteins, myelin, and inflammatory cells were analyzed in parallel.

Results

KIR4.1 is expressed in oligodendrocytes and astrocytes in the adult human brain. In oligodendrocytes, KIR4.1 appears as a homotetramer channel, in astrocytes as homo‐ and heterotetramer channels together with KIR5.1. In acute MS lesions, KIR4.1 immunoreactivity (IR) was differentially lost on periplaque oligodendrocytes and perivascular astrocytes. In part of acute lesions, complement activation, apoptotic KIR4.1+ glial cells, and phagocytes containing KIR4.1+ fragments accompanied loss of glial KIR4.1 IR. Periplaque reactive astrocytes showed enhanced IR for both KIR4.1 and KIR5.1. In chronic active MS lesions, apart from a general loss of oligodendrocytes in the demyelinated area, we observed a decrease of astroglial KIR4.1 but not glial fibrillary acidic protein IR. In chronic inactive and remyelinating MS lesions, KIR4.1 IR was restored on astrocytes and found in a subset of presumably new myelinating oligodendrocytes.

Interpretation

The expression profile of KIR4.1 in glial cells and stage‐dependent alterations of KIR4.1 IR in MS lesions are compatible with an immune response against KIR4.1 at least in a subset of MS patients. Ann Neurol 2014;75:810–828
Redox Chemistry of a Hydroxyphenyl‐Substituted Borane
Authors: Feng Po‐Yeng , Liu Yi‐Hung , Lin Tien‐Sung , Peng Shie‐Ming , Chiu Ching‐Wen
Published: April 2014

Chemical reduction of a hydroxyphenyl‐substituted borane triggers a sequential electron‐ and intramolecular hydrogen‐atom‐transfer process to afford a hydridoborate phenoxide dianion. On the other hand, hydrogen‐atom abstraction of the borane leads to the isolation of a neutral borylated phenoxyl radical, which can be transformed to the corresponding benzoquinone borataalkene derivative by reduction with cobaltocene.
Asymmetric [5+3] Formal Cycloadditions with Cyclic Enones through Cascade Dienamine–Dienamine Catalysis
Authors: Yin Xiang , Zheng Yi , Feng Xin , Jiang Kun , Wei Xue‐Zhen , Gao Ning , Chen Ying‐Chun
Published: April 2014

A few aminocatalytic modes, such as iminium ions and different dienamines, have provided versatile tools for the functionalization of cyclic enones at various sites. Described here is a previously unreported cascade dienamine/dienamine catalytic pathway for β‐substituted 2‐cyclopentenones, and even 2‐cyclohexenone. It involves domino α′‐regioselective Michael addition and a γ‐regioselective Mannich reaction with 3‐vinyl‐1,2‐benzoisothiazole‐1,1‐dioxides to give fused or bridged architectures, which incorporate a spirocyclic skeleton, in excellent stereocontrol, thus furnishing unusual [5+3] formal cycloaddition reactions. Moreover, preliminary biological assays showed that some of the chiral products exhibited promising activity against some cancer cell lines, thus indicating that such skeletons might serve as leads in drug discovery.
A Metal‐Bridged Tricyclic Aromatic System: Synthesis of Osmium Polycyclic Aromatic Complexes
Authors: Zhu Congqing , Zhu Qin , Fan Jinglan , Zhu Jun , He Xumin , Cao Xiao‐Yu , Xia Haiping
Published: April 2014

Aromaticity is one of the most important concepts in organic chemistry. A variety of metalla‐aromatic compounds have been recently prepared and in most of those examples, the metal participates only in a monocyclic ring. In contrast, metal‐bridged bicyclic aromatic molecules, in which a metal is shared between two aromatic rings, have been less developed. Herein, we report the first metal‐bridged tricyclic aromatic system, in which the metal center is shared by three aromatic five‐membered rings. These metalla‐aromatics are formed by reaction between osmapentalyne and arene nucleophiles. Experimental results and theoretical calculations reveal that the three five‐membered rings around the osmium center are aromatic. In addition, the broad absorption bands in the UV/Vis absorption spectra of these novel aromatic systems cover almost the entire visible region. This straightforward synthetic strategy may be extended to the synthesis of other metal‐bridged polycyclic aromatics.
X‐ray crystal structures and MMA polymerization of cadmium(II) complexes with bidentate pyrazole ligands: the formation of monomers or dimers as a function of a methyl substituent on the pyrazole and aniline rings
Authors: Kim Dongil , Kim Sunghoon , Woo Hyun Yul , Lee Ha‐Jin , Lee Hyosun
Published: April 2014

The reaction of CdBr2·4H2O with ancillary ligands, N,N‐bis(1H‐pyrazolyl‐1‐methyl)aniline (L1), N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐p‐methylaniline (L2), N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐3,5‐dimethylaniline (L3), N,N‐bis(3,5‐dimethyl‐1H‐pyrazolyl‐1‐methyl)aniline (L4) and N,N‐bis(1H‐pyrazolyl‐1‐methyl)‐2,6‐dimethylaniline (L5) in ethanol yields novel Cd(II) bromide complexes, [L1CdBr2]2, [L2CdBr2]2, [L3CdBr2]2, [L4CdBr2] and [L5CdBr2]. The X‐ray crystal structures of [L1CdBr2]2, [L2CdBr2]2 and [L3CdBr2]2 reveal a bromo‐bridged dimeric species with crystallographic inversion symmetry. Conversely, [L4CdBr2] and [L5CdBr2] exist as monomeric complexes, presumably due to the steric hindrance between the methyl substituents of the two pyrazole groups in the ligand and cadmium centre for [L4CdBr2], and crowding around the cadmium metal by methyl substituents on the aniline residue in the ligand for [L5CdBr2]. The geometry at each Cd(II) centre for [L1CdBr2]2, [L2CdBr2]2 and [L3CdBr2]2 is best described as a distorted trigonal bipyramid. A distorted trigonal bipyramid is achieved in [L4CdBr2] by coordinative interaction of the nitrogen atom of the aniline unit and the cadmium atom with a σ plane of symmetry, based on the bond length of Cd―Naniline (2.759(7) Å). [L5CdBr2] exists with a distorted tetrahedral geometry involving non‐coordination of the nitrogen atom of aniline and the Cd centre, resulting in the formation of an eight‐membered chelate ring. The catalytic activity of monomeric, five‐coordinated [L4CdBr2] in the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) at 60°C resulted in a higher molecular weight and a narrower polydispersity index (PDI) than those obtained with dimeric [LnCdBr2]2 (Ln = L1, L2, L3) or monomeric tetrahedral [L5CdBr2]. Copyright © 2014 John Wiley & Sons, Ltd.
Mechanical and thermal properties of hierarchical composites enhanced by pristine graphene and graphene oxide nanoinclusions
Authors: Zhang B. , Asmatulu R. , Soltani S. A. , Le L. N. , Kumar S. S. A.
Published: April 2014

Epoxy resin nanocomposites incorporated with 0.5, 1, 2, and 4 wt % pristine graphene and modified graphene oxide (GO) nanoflakes were produced and used to fabricate carbon fiber‐reinforced and glass fiber‐reinforced composite panels via vacuum‐assisted resin transfer molding process. Mechanical and thermal properties of the composite panels—called hierarchical graphene composites—were determined according to ASTM standards. It was observed that the studied properties were improved consistently by increasing the amount of nanoinclusions. Particularly, in the presence of 4 wt % GO in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 15% (21%), 34% (84%), and 40% (68%), respectively. Likewise, with inclusion of 4 wt % pristine graphene in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 11% (7%), 30% (77%), and 34% (58%), respectively. Also, thermal conductivity of the carbon fiber (glass fiber) composites with 4% GO inclusion was improved 52% (89%). Similarly, thermal conductivity of the carbon fiber (glass fiber) composites with 4% pristine graphene inclusion was improved 45% (80%). The reported results indicate that both pristine graphene and modified GO nanoflakes are excellent options to enhance the mechanical and thermal properties of fiber‐reinforced polymeric composites and to make them viable replacement materials for metallic parts in different industries, such as wind energy, aerospace, marine, and automotive. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40826.
CONTACTING IS ESSENTIAL FOR OVIPOSITION DETERRENCE OF RHODOJAPONIN‐III IN SPODOPTERA LITURA
Authors: Yi Xin , Liu Jinxiang , Wang Peidan , Hu Meiying , Zhong Guohua
Published: April 2014

In Lepidoptera, choosing the right site for egg laying is particularly important, because the small larvae cannot forage for alternate host plants easily. Some secondary compounds of plants have the ability to deter oviposition behaviors of insects. Rhodojaponin‐III, a botanical compound, has been reported to have intense deterring‐oviposition activity against many insects, which have important implications for agricultural pest management. This study provided evidence for elucidating the perception mechanism underlying Rhodojaponin‐III as oviposition deterrent. In this study, the antennas of moths could not elicit notable electroantennogram responses to Rhodojaponin‐III, which suggested the Rhodojaponin‐III could not exert effects like those volatile compounds. The results of physiological experiments confirmed the Rhodojaponin‐III could produce the oviposition deterrence effect against moths without depending on antennas, while the physical contact was essential for perceiving the compound, which suggested that the sensilla on tarsus and ovipositor could be chemoreceptor for Rhodojaponin‐III. Therefore, these sensilla were investigated by scanning electron microscopy to explore their potential functions in detecting Rhodojaponin‐III. This study highlighted the contacting mechanism in deterring oviposition behaviors of moths by Rhodojaponin‐III and provided new insight for development of contact‐based pest management.
Macrophage Migration Inhibitory Factor Inhibits the Antiinflammatory Effects of Glucocorticoids via Glucocorticoid‐Induced Leucine Zipper
Authors: Fan Huapeng , Kao Wenping , Yang Yuan H. , Gu Ran , Harris James , Fingerle‐Rowson Günter , Bucala Richard , Ngo Devi , Beaulieu Elaine , Morand Eric F.
Published: April 2014

Objective

Glucocorticoids remain a mainstay in the treatment of rheumatoid arthritis (RA). Dose‐dependent adverse effects highlight the need for therapies that regulate glucocorticoid sensitivity to enable dosage reduction. Macrophage migration inhibitory factor (MIF) is a proinflammatory protein that has been implicated in the pathogenesis of RA; it impairs glucocorticoid sensitivity via MAPK phosphatase 1 (MKP‐1) inhibition. The intracellular protein glucocorticoid‐induced leucine zipper (GILZ) mimics the effects of glucocorticoids in models of RA, but whether it represents a target for the modulation of glucocorticoid sensitivity remains unknown. We undertook this study to investigate whether GILZ is involved in the regulation of glucocorticoid sensitivity by MIF.

Methods

GILZ expression was studied in the presence and absence of MIF, and the role of GILZ in the MIF‐dependent regulation of the glucocorticoid sensitivity mediator MKP‐1 was studied at the level of expression and function.

Results

GILZ expression was significantly inhibited by endogenous MIF, both basally and during responses to glucocorticoid treatment. The effects of MIF on GILZ were dependent on the expression and Akt‐induced nuclear translocation of the transcription factor FoxO3A. GILZ was shown to regulate the expression of MKP‐1 and consequent MAPK phosphorylation and cytokine release.

Conclusion

MIF exerts its effects on MKP‐1 expression and MAPK activity through inhibitory effects on GILZ. These findings suggest a previously unsuspected interaction between MIF and GILZ and identify GILZ as a potential target for the therapeutic regulation of glucocorticoid sensitivity.
The Structural Diversity of Benzofuran Resorcinarene Leads to Enhanced Fluorescence
Authors: Tero Tiia‐Riikka , Salorinne Kirsi , Lehtivuori Heli , Ihalainen Janne A. , Nissinen Maija
Published: April 2014

An unexpected and previously unknown resorcinarene mono‐crown with a fused benzofuran moiety in its macrocyclic core was obtained as a byproduct from a bridging reaction of tetramethoxy resorcinarene with tetraethylene glycol ditosylate. The formation of the fused benzofuran moiety in the resorcinarene macrocycle resulted in a unique rigid and puckered boat conformation, as shown by XRD studies in the solid state. Modification of the macrocycle was also observed to affect the photophysical properties in solution by enhancing the fluorescence brightness compared with a conventional resorcinarene macrocycle. The fluorescent properties enabled unique detection of structural features, that is, the rigid boat conformation with the conjugated benzofuran system and the more flexible crown bridge part, in solution.
Improving reasoning skills in secondary history education by working memory training
Authors: Ariës Roel Jacobus , Groot Wim , van den Brink Henriette Maassen
Published: April 2014

Secondary school pupils underachieve in tests in which reasoning abilities are required. Brain‐based training of working memory (WM) may improve reasoning abilities. In this study, we use a brain‐based training programme based on historical content to enhance reasoning abilities in history courses. In the first experiment, a combined intervention of WM‐capacity and reasoning strategies is trained and compared with control group data in ‘HAVO’ (medium track secondary education in the Netherlands). WM‐capacity and reasoning strategies of the experimental group improve significantly after three weeks of training. Students achieve significantly better in school tests in which reasoning abilities are tested. The gain in reasoning abilities is also significant 16 weeks after the training programme is completed. In the second experiment, WM‐capacity and reasoning strategies are trained independently and compared with control group data in ‘VWO’ (upper track secondary education). Training of WM‐capacity did not improve achievements in reasoning tests significantly, but training of reasoning strategies did. However, the results of both experiments cannot be compared because of cognitive group differences between Experiment 1 and 2 (educational tracks). These results demonstrate that brain‐based learning strategies to improve reasoning abilities can easily be integrated in history curricula. Furthermore, a six‐week training period can improve reasoning abilities of students in secondary education significantly. The study used content‐based, non‐adaptive training methods that are based on standardised tests. Cognitive WM test scores indicate a ceiling effect which can be explained by the absence of the adaptive element in the training.
The socio‐economic gradient in children's reading skills and the role of genetics
Authors: Jerrim John , Vignoles Anna , Lingam Raghu , Friend Angela
Published: April 2014

By the time children leave primary school there is a large socio‐economic gap in their reading proficiency. There are a number of potential explanations for this socio‐economic gap and in this paper we investigate the role of three particular genes and gene–environment interactions in determining children's reading skills, using the Avon Longitudinal Study of Parents and Children (ALSPAC) dataset. We find that whilst these genes are indeed correlated with reading outcomes, effect sizes are small and sensitive to the choice of test used and the sample selected. Our results suggest that these leading candidate genes can jointly explain just 2% of the socio‐economic gap in children's reading test scores. We conclude that the influence of these three genes on children's reading ability is limited, and their role in producing socio‐economic gaps in reading ability is even more limited still.
European do‐it‐yourself (DIY) biology: Beyond the hope, hype and horror
Authors: Seyfried Günter , Pei Lei , Schmidt Markus
Published: April 2014

The encounter of amateur science with synthetic biology has led to the formation of several amateur/do‐it‐yourself biology (DIYBio) groups worldwide. Although media outlets covered DIYBio events, most seemed only to highlight the hope, hype, and horror of what DIYBio would do in the future. Here, we analyze the European amateur biology movement to find out who they are, what they aim for and how they differ from US groups. We found that all groups are driven by a core leadership of (semi‐)professional people who struggle with finding lab space and equipment. Regulations on genetic modification limit what groups can do. Differences between Europe and the US are found in the distinct regulatory environments and the European emphasis on bio‐art. We conclude that DIYBio Europe has so far been a responsible and transparent citizen science movement with a solid user base that will continue to grow irrespective of media attention.
Keeping your armour intact: How HIV‐1 evades detection by the innate immune system
Authors: Maelfait Jonathan , Seiradake Elena , Rehwinkel Jan
Published: April 2014

HIV‐1 infects dendritic cells (DCs) without triggering an effective innate antiviral immune response. As a consequence, the induction of adaptive immune responses controlling virus spread is limited. In a recent issue of Immunity, Lahaye and colleagues show that intricate interactions of HIV capsid with the cellular cofactor cyclophilin A (CypA) control infection and innate immune activation in DCs. Manipulation of HIV‐1 capsid to increase its affinity for CypA results in reduced virus infectivity and facilitates access of the cytosolic DNA sensor cGAS to reverse transcribed DNA. This in turn induces a strong host response. Here, we discuss these findings in the context of recent developments in innate immunity and consider the implications for disease control and vaccine design.
AN EVALUATION OF SELF‐MONITORING TO IMPROVE SWIMMING PERFORMANCE
Authors: Schonwetter Sara W. , Miltenberger Raymond , Oliver Jeffrey R.
Published: April 2014

This study evaluated the effects of self‐monitoring by swimmers to improve their performance and assessed the effects of reactivity to observer presence on their performance. Seven public high school swim team members self‐monitored their behavior on dry erase boards to increase the number of assigned laps completed at practice. Reactivity to observer presence was assessed as a confederate, recorded the number of laps completed during observer absent conditions. The percentage of assigned laps completed increased during the self‐monitoring phases. The self‐monitoring and feedback phase further increased the percentage of assigned laps completed and increased the participants' mean level of reporting accuracy. The effects from the reactivity assessment were mixed across participants. Further research is needed to examine reactivity effects in sport settings. Copyright © 2014 John Wiley & Sons, Ltd.
Terrorism in Pakistan: A Behavioral Sciences Perspective
Authors: Nizami Asad Tamizuddin , Rana Mowadat Hussain , Hassan Tariq Mahmood , Minhas Fareed Aslam
Published: April 2014

This article reviews the behavioral science perspectives of terrorism in Pakistan. It can be argued that Pakistan has gained worldwide attention for “terrorism” and its role in the “war against terrorism”. The region is well placed geopolitically for economic successes but has been plagued by terrorism in various shapes and forms. A behavioral sciences perspective of terrorism is an attempt to explain it in this part of the world as a complex interplay of historical, geopolitical, anthropological and psychosocial factors and forces. Drawing from theories by Western scholars to explain the behavioral and cognitive underpinnings of a terrorist mind, the authors highlight the peculiarities of similar operatives at individual and group levels. Thorny issues related to the ethical and human right dimensions of the topic are visited from the unique perspective of a society challenged by schisms and divergence of opinions at individual, family, and community levels. The authors have attempted to minimize the political descriptions, although this cannot be avoided entirely, because of the nature of terrorism. Copyright © 2014 John Wiley & Sons, Ltd.
Complete response after autologous stem cell transplant in multiple myeloma
Authors: Kumar Lalit , Iqbal Nida , Mookerjee Anjali , Verma Rakesh Kumar , Sharma Om D. , Batra Atul , Pramanik Raja , Gupta Ritu
Published: April 2014

We evaluated long‐term outcome of patients achieving complete response (CR) after autologous stem cell transplantation (ASCT) for multiple myeloma. Between April 1990 and June 2012 191 patients underwent ASCT. The median age was 53 years (range, 26–68 years), 135 were men. Pretransplant, patients received induction therapy with VAD (vincristine, doxorubicin, dexamethasone; n = 77), novel agents (n = 92), or alkylating agent‐based, n = 22); 43% received more than one line of induction regimen. Response to transplant was defined as per EBMT criteria. The median follow‐up for the entire group was 85 months (range, 6–232.5 months). Following transplant 109 (57.1%) patients achieved CR. Median progression‐free survival (PFS) for patients with CR was higher compared to those with VGPR and PR, (107 vs. 18 vs. 18 months, P < 0.001). Number of lines of therapy pretransplant (one or two vs. more than two lines of therapy (P < 0.001), and absolute lymphocyte count of ≤3000/cmm were predictors of superior PFS. Median overall survival (OS) for patients with CR was higher, (204 months), compared to those with VGPR (71.5 months, P < 0.001) and PR (51.5 months, P < 0.001), respectively. On Cox regression analysis, patients who received one line of induction therapy pretransplant (hazard ratio, HR 2.154, P < 0.001) and those with absolute lymphocyte count of ≤3000/mm3 (HR 0.132, P < 0.001) had superior PFS. For overall survival, induction treatment up to one line (HR 2.403, P < 0.004) and Hb > 7.1 G/dL at diagnosis (HR 4.756, P < 0.01) were associated with superior outcome. On landmark analysis at 12 months, PFS and OS continued to remain superior for patients attaining CR. Achievement of CR post transplant is associated with longer OS and PFS. Among complete responders, those who receive one line of induction therapy pretransplant have superior outcome.
Small‐Molecule Proteomimetic Inhibitors of the HIF‐1α–p300 Protein–Protein Interaction
Authors: Burslem George M. , Kyle Hannah F. , Breeze Alexander L. , Edwards Thomas A. , Nelson Adam , Warriner Stuart L. , Wilson Andrew J.
Published: April 2014

The therapeutically relevant hypoxia inducible factor HIF‐1α–p300 protein–protein interaction can be orthosterically inhibited with α‐helix mimetics based on an oligoamide scaffold that recapitulates essential features of the C‐terminal helix of the HIF‐1α C‐TAD (C‐terminal transactivation domain). Preliminary SAR studies demonstrated the important role of side‐chain size and hydrophobicity/hydrophilicity in determining potency. These small molecules represent the first biophysically characterised HIF‐1α–p300 PPI inhibitors and the first examples of small‐molecule aromatic oligoamide helix mimetics to be shown to have a selective binding profile. Although the compounds were less potent than HIF‐1α, the result is still remarkable in that the mimetic reproduces only three residues from the 42‐residue HIF‐1α C‐TAD from which it is derived.
Involvement of SgvP in Carbon–Sulfur Bond Formation during Griseoviridin Biosynthesis
Authors: Xie Yunchang , Li Qinglian , Song Yongxiang , Ma Junying , Ju Jianhua
Published: April 2014

Griseoviridin (GV) is an A‐type streptogramin antibiotic displaying antimicrobial activity and acting synergistically with viridogrisein (VG). Bioinformatic analyses reveal SgvP as the sole cytochrome P450 enzyme in the GV/VG gene cluster. To explore the role of SgvP in the GV/VG pathway, we inactivated the sgvP gene. The resulting ΔsgvP mutant generated two new products: GV‐1 and GV‐2, both lacking the CS bridge. In trans complementation of the sgvP gene into the ΔsgvP mutant strain partially restores GV production. Feeding [1‐13C]‐labeled cysteine to the wild‐type strain led to enrichment of C‐7 in the GV scaffold, thus verifying that the CS bond in GV is formed through direct coupling of the free SH group provided by the side chain of cysteine. The above results highlight the significance of SgvP in CS bond formation in griseoviridin biosynthesis.
Magnifying the Morphology Change Induced by a Nickel Promoter in Tungsten(IV) Sulfide Industrial Hydrocracking Catalyst: A HAADF‐STEM and DFT Study
Authors: Girleanu Maria , Alphazan Thibault , Boudene Zoubeyr , Bonduelle‐Skrzypczak Audrey , Legens Christèle , Gay Anne‐Sophie , Copéret Christophe , Ersen Ovidiu , Raybaud Pascal
Published: April 2014

Changes in the two‐dimensional (2D) morphology of nonpromoted WS2 and Ni‐promoted WS2 (NiWS) catalytically active nanolayers supported on amorphous silica‐alumina (ASA) are revealed by aberration‐corrected scanning transmission electron microscopy and rationalized by density functional theory calculations. The presence of the Ni atoms modifies the triangular shape of nonpromoted WS2/ASA nanolayers into a more hexagonal one for NiWS/ASA by stabilizing the S edge more strongly than the W edge. The higher catalytic activity induced by the addition of the promoter confirms the relevance of such a morphology effect for industrial catalysts.
Three‐Dimensional Structural Engineering for Energy‐Storage Devices: From Microscope to Macroscope
Authors: Xu Jing , Wang Xianfu , Wang Xiaowei , Chen Di , Chen Xiaoyuan , Li Dongdong , Shen Guozhen
Published: April 2014

For high‐performance energy‐storage devices, three‐dimensional (3D) designs with diverse configurations are demonstrated to provide highly qualified electrodes and efficient device integration. From a microscope to a macroscope view, this review summarizes the recent advances in electrochemically active nanomaterials, novel current collectors, and integrations of the devices in 3D configurations.
The Nature of the Fourth Bond in the Ground State of C2: The Quadruple Bond Conundrum
Authors: Danovich David , Hiberty Philippe C. , Wu Wei , Rzepa Henry S. , Shaik Sason
Published: April 2014

Does, or doesn’t C2 break the glass ceiling of triple bonding? This work provides an overview on the bonding conundrum in C2 and on the recent discussions regarding our proposal that it possesses a quadruple bond. As such, we focus herein on the main point of contention, the 4th bond of C2, and discuss the main views. We present new data and an overview of the nature of the 4th bond—its proposed antiferromagnetically coupled nature, its strength, and a derivation of its bond energy from experimentally based thermochemical data. We address the bond‐order conundrum of C2 arising from generalized VB (GVB) calculations by comparing it to HCCH, and showing that the two molecules behave very similarly, and C2 is in no way an exception. We analyse the root cause of the deviation of C2 from the Badger Rule, and demonstrate that the reason for the smaller force constant (FC) of C2 relative to HCCH has nothing to do with the bond energies, or with the number of bonds in the two molecules. The FC is determined primarily by the bond length, which is set by the balance between the bond length preferences of the σ‐ versus π‐bonds in the two molecules. This interplay in the case of C2 clearly shows the fingerprints of the 4th bond. Our discussion resolves the points of contention and shows that the arguments used to dismiss the quadruple bond nature of C2 are not well founded.
Binding of a Ruthenium Complex to a Thioether Ligand Embedded in a Negatively Charged Lipid Bilayer: A Two‐Step Mechanism
Authors: Bahreman Azadeh , Rabe Martin , Kros Alexander , Bruylants Gilles , Bonnet Sylvestre
Published: April 2014

The interaction between the ruthenium polypyridyl complex [Ru(terpy)(dcbpy)(H2O)]2+ (terpy=2,2′;6′,2“‐terpyridine, dcbpy=6,6′‐dichloro‐2,2′‐bipyridine) and phospholipid membranes containing either thioether ligands or cholesterol were investigated using UV–visible spectroscopy, Langmuir–Blodgett monolayer surface pressure measurements, and isothermal titration calorimety (ITC). When embedded in a membrane, the thioether ligand coordinated to the dicationic metal complex only when the phospholipids of the membrane were negatively charged, that is, in the presence of attractive electrostatic interaction. In such a case coordination is much faster than in homogeneous conditions. A two‐step model for the coordination of the metal complex to the membrane‐embedded sulfur ligand is proposed, in which adsorption of the complex to the negative surface of the monolayers or bilayers occurs within minutes, whereas formation of the coordination bond between the surface‐bound metal complex and ligand takes hours. Finally, adsorption of the aqua complex to the membrane is driven by entropy. It does not involve insertion of the metal complex into the hydrophobic lipid layer, but rather simple electrostatic adsorption at the water–bilayer interface.
Ruthenium Complexes of an Abnormally Bound, Anionic N‐Heterocyclic Carbene
Authors: Pranckevicius Conor , Stephan Douglas W.
Published: April 2014

The abnormally bound, anionic NHC–borane complex [Ru(IDipp‐BF3)(p‐cymene)Cl]2 (4; IDipp‐BF3=1,3‐(2,6‐iPr2C6H3)2‐2‐BF3(C3HN2)‐4‐yl) was synthesized by transmetalation from Li[(IDipp‐BF3)2Ag]. Addition of donors gave species of the form [Ru(IDipp‐BF3)(p‐cymene)(L)Cl], whereas halide abstraction with Ag(Et2O)[B(C6F5)4] gave CH activation of the methine position of the IDippBF3 ligand.
Synthesis of Cyclobutenes and Allenes by Cobalt‐Catalyzed Cross‐Dimerization of Simple Alkenes with 1,3‐Enynes
Authors: Nishimura Akira , Tamai Eri , Ohashi Masato , Ogoshi Sensuke
Published: April 2014

Cobalt‐catalyzed cross‐dimerization of simple alkenes with 1,3‐enynes is reported. A [2+2] cycloaddition reaction occurred, with alkenes bearing no allylic hydrogen, by reductive elimination of a η3‐butadienyl cobaltacycle. On the other hand, aliphatic alkenes underwent 1,4‐hydroallylation by means of exo‐cyclic β‐H elimination. These reactions can provide cyclobutenes and allenes that were previously difficult to access, from simple substrates in a highly chemo‐ and regioselective manner.
Evidence of Noncentrosymmetry of Human Tooth Hydroxyapatite Crystals
Authors: Mugnaioli Enrico , Reyes‐Gasga José , Kolb Ute , Hemmerlé Joseph , Brès Étienne F.
Published: April 2014

Herein, we investigate human single hydroxyapatite crystals (enamel and dentine) by convergent‐beam electron diffraction (CBED) and automated electron‐diffraction tomography (ADT). The CBED pattern shows the absence of the mirror plane perpendicular to the c axis leading to the P63 space group instead of the P63/m space group considered for larger‐scale crystals, this is confirmed by ADT. This experimental evidence is of prime importance for understanding the morphogenesis and the architectural organization of calcified tissues.
Linking an α‐Tocopherol Derivative to Cobalt(0) Nanomagnets: Magnetically Responsive Antioxidants with Superior Radical Trapping Activity and Reduced Cytotoxicity
Authors: Viglianisi Caterina , Di Pilla Veronica , Menichetti Stefano , Rotello Vincent M. , Candiani Gabriele , Malloggi Chiara , Amorati Riccardo
Published: April 2014

Covalent attachment of a phenolic antioxidant analogue of α‐tocopherol to graphite‐coated magnetic cobalt nanoparticles (CoNPs) provided a novel magnetically responsive antioxidant capable of preventing the autoxidation of organic materials and showing a reduced toxicity toward human cells.
Asymmetric Synthesis of Fortucine and Reassignment of Its Absolute Configuration
Authors: Beaulieu Marc‐André , Ottenwaelder Xavier , Canesi Sylvain
Published: April 2014

A convergent and enantioselective synthesis of fortucine was achieved from the starting materials tyrosine methyl ester and 3‐hydroxy‐4‐methoxybenzaldehyde. The synthesis is based on two key steps mediated by a hypervalent iodine reagent. This work has enabled us to reassign the absolute configuration of the natural product reported in the literature.
Solvent‐Dependent Cation Exchange in Metal–Organic Frameworks
Authors: Brozek Carl K. , Bellarosa Luca , Soejima Tomohiro , Clark Talia V. , López Núria , Dincă Mircea
Published: April 2014

We investigated which factors govern the critical steps of cation exchange in metal–organic frameworks by studying the effect of various solvents on the insertion of Ni2+ into MOF‐5 and Co2+ into MFU‐4l. After plotting the extent of cation insertion versus different solvent parameters, trends emerge that offer insight into the exchange processes for both systems. This approach establishes a method for understanding critical aspects of cation exchange in different MOFs and other materials.
Two‐Dimensional Tetrathiafulvalene Covalent Organic Frameworks: Towards Latticed Conductive Organic Salts
Authors: Jin Shangbin , Sakurai Tsuneaki , Kowalczyk Tim , Dalapati Sasanka , Xu Fei , Wei Hao , Chen Xiong , Gao Jia , Seki Shu , Irle Stephan , Jiang Donglin
Published: April 2014

The construction of a new class of covalent TTF lattice by integrating TTF units into two‐dimensional covalent organic frameworks (2D COFs) is reported. We explored a general strategy based on the C2+C2 topological diagram and applied to the synthesis of microporous and mesoporous TTF COFs. Structural resolutions revealed that both COFs consist of layered lattices with periodic TTF columns and tetragonal open nanochannels. The TTF columns offer predesigned pathways for high‐rate hole transport, predominate the HOMO and LUMO levels of the COFs, and are redox active to form organic salts that exhibit enhanced electric conductivity by several orders of magnitude. On the other hand, the linkers between the TTF units play a vital role in determining the carrier mobility and conductivity through the perturbation of 2D sheet conformation and interlayer distance. These results open a way towards designing a new type of TTF materials with stable and predesignable lattice structures for functional exploration.
Development of 3‐Phenyl‐N‐(2‐(3‐phenylureido)ethyl)‐thiophene‐2‐sulfonamide Compounds as Inhibitors of Antiapoptotic Bcl‐2 Family Proteins
Authors: Yang Chengwen , Chen Sha , Zhou Mi , Li Yan , Li Yangfeng , Zhang Zhengxi , Liu Zhen , Ba Qian , Li Jingquan , Wang Hui , Yan Xiaomei , Ma Dawei , Wang Renxiao
Published: April 2014

Antiapoptotic Bcl‐2 family proteins, such as Bcl‐xL, Bcl‐2, and Mcl‐1, are often overexpressed in tumor cells, which contributes to tumor cell resistance to chemotherapies and radiotherapies. Inhibitors of these proteins thus have potential applications in cancer treatment. We discovered, through structure‐based virtual screening, a lead compound with micromolar binding affinity to Mcl‐1 (inhibition constant (Ki)=3 μM). It contains a phenyltetrazole and a hydrazinecarbothioamide moiety, and it represents a structural scaffold not observed among known Bcl‐2 inhibitors. This work presents the structural optimization of this lead compound. By following the scaffold‐hopping strategy, we have designed and synthesized a total of 82 compounds in three sets. All of the compounds were evaluated in a fluorescence‐polarization binding assay to measure their binding affinities to Bcl‐xL, Bcl‐2, and Mcl‐1. Some of the compounds with a 3‐phenylthiophene‐2‐sulfonamide core moiety showed sub‐micromolar binding affinities to Mcl‐1 (Ki=0.3–0.4 μM) or Bcl‐2 (Ki≈1 μM). They also showed obvious cytotoxicity on tumor cells (IC50<10 μM). Two‐dimensional heteronuclear single quantum coherence NMR spectra of three selected compounds, that is, YCW‐E5, YCW‐E10, and YCW‐E11, indicated that they bind to the BH3‐binding groove on Bcl‐xL in a similar mode to ABT‐737. Several apoptotic assays conducted on HL‐60 cells demonstrated that these compounds are able to induce cell apoptosis through the mitochondrial pathway. We propose that the compounds with the 3‐phenylthiophene‐2‐sulfonamide core moiety are worth further optimization as effective apoptosis inducers with an interesting selectivity towards Mcl‐1 and Bcl‐2.
Monoamine Oxidase (MAO) Inhibitory Activity: 3‐Phenylcoumarins versus 4‐Hydroxy‐3‐phenylcoumarins
Authors: Delogu Giovanna L. , Serra Silvia , Quezada Elias , Uriarte Eugenio , Vilar Santiago , Tatonetti Nicholas P. , Viña Dolores
Published: April 2014

Monoamine oxidase (MAO) is a useful target in the treatment of neurodegenerative diseases and depressive disorders. Both isoforms, MAO‐A and MAO‐B, are known to play critical roles in disease progression, and as such, the identification of novel, potent and selective inhibitors is an important research goal. Here, two series of 3‐phenylcoumarin derivatives were synthesized and evaluated against MAO‐A and MAO‐B. Most of the compounds tested acted preferentially on MAO‐B, with IC50 values in the micromolar to nanomolar range. Only 6‐chloro‐4‐hydroxy‐3‐(2’‐hydroxyphenyl)coumarin exhibited activity against the MAO‐A isoform, while still retaining good selectivity for MAO‐B. 6‐Chloro‐3‐phenylcoumarins unsubstituted at the 4 position were found to be more active as MAO‐B inhibitors than the corresponding 4‐hydroxylated coumarins. For 4‐unsubstituted coumarins, meta and para positions on the 3‐phenyl ring seem to be the most favorable for substitution. Molecular docking simulations were used to explain the observed hMAO‐B structure–activity relationships for this type of compound. 6‐Chloro‐3‐(3’‐methoxyphenyl)coumarin was the most active compound identified (IC50=0.001 μM) and is several times more potent and selective than the reference compound, R‐(−)‐deprenyl hydrochloride. This compound represents a novel tool for the further investigation of the therapeutic potential of MAO‐B inhibitors.
Science gateway technologies for the astrophysics community
Authors: Becciani Ugo , Sciacca Eva , Costa Alessandro , Massimino Piero , Pistagna Costantino , Riggi Simone , Vitello Fabio , Petta Catia , Bandieramonte Marilena , Krokos Mel
Published: April 2014

The availability of large‐scale digital surveys offers tremendous opportunities for advancing scientific knowledge in the astrophysics community. Nevertheless, the analysis of these data often requires very powerful computational resources. Science gateway technologies offer Web‐based environments to run applications with little concern for learning and managing the underlying infrastructures that execute them. This paper focuses on the issues related to the development of a science gateway customized for the needs of the astrophysics community. The VisIVO Science Gateway is wrapped around a WS‐PGRADE/grid User Support Environment portal integrating services for processing and visualizing large‐scale multidimensional astrophysical data sets on distributed computing infrastructures. We discuss the core tools and services supported including an application for mobile access to the gateway. We report our experiences in supporting specialized astrophysical communities requiring development of complex workflows for visualization and numerical simulations. Further, available platforms are discussed for sharing workflows in collaborative environments. Finally, we outline our vision for creating a federation of science gateways to benefit astrophysical communities by sharing a set of services for authentication, computing infrastructure access and data/workflow repositories. Copyright © 2014 John Wiley & Sons, Ltd.
Efficient privacy preserving matchmaking for mobile social networking
Authors: Wang Yong , Hou Jie , Xia Yun , Li Hong‐zong
Published: April 2014

Discovering new friends who share common attributes, named as matchmaking, is one of the most popular applications in mobile social networking. The key security issue in matchmaking is to protect users' personal information. In this paper, we propose a novel privacy preserving matchmaking framework, which can help users to find new friends in mobile social networking without leaking their privacy information. A user (called initiator) can find the one who shares maximum number of common attributes with him (called best match) among nearby users (called candidates), and only exchange an attribute intersection set with the best match, while other candidates only know the size of the attribute intersection set mutually. The analysis and simulation results show that our protocol can resist both semi‐honest and malicious attacks while providing efficient matchmaking functionality. Copyright © 2014 John Wiley & Sons, Ltd.
Improving the program performance through prioritized memory management and disk operation
Authors: Yeh Tsozen , Yang Shuwen , Sun Yifeng
Published: April 2014

Computers are indispensable to modern human society. Often, computers host multiple programs running simultaneously. However, among those programs, some maybe more time critical than others to users. Consequently, users would hope those time‐critical programs to finish their execution as soon as possible. Generally speaking, the course of program execution includes cooperative operation of CPU, memory, and hard disk. For CPU operation, modern computer systems have the ability to adjust the CPU scheduling sequence according to program priority. Nevertheless, most of them do not have effective ways to provide memory management and disk operation based on program priority. Consequently, it is hard to speed up the execution of prioritized programs as users would expect. The Linux operating system has been widely used in recent years. Even though it still does not support fully‐prioritized memory management and disk operation. Previously, based on the default Linux disk scheduler, complete fair queuing (CFQ), we proposed a new disk scheduling algorithm called prioritized CFQ (PCFQ) to provide fully‐prioritized disk operation. PCFQ had demonstrated good performance improvement for programs with high priority. In this paper, we report our effort to integrate PCFQ with prioritized memory management as a whole in the Linux operating system. With the cooperation between prioritized memory management and prioritized disk operation, our system further enhanced the performance that PCFQ achieved by up to 62.08%. Experimental results also showed that, compared with the current Linux system, our design can lift the performance of individual prioritized programs by up to 76.63% when there was one prioritized program on the system. The number went up to 82.45% when the system hosted three programs with high priority.Concurrency and Computation: Practice and Experience.Copyright © 2014 John Wiley & Sons, Ltd.
Quantum Chemical Studies on Solvents for Post‐Combustion Carbon Dioxide Capture: Calculation of pKa and Carbamate Stability of Disubstituted Piperazines
Authors: Gangarapu Satesh , Wierda Gerben J. , Marcelis Antonius T. M. , Zuilhof Han
Published: April 2014

Piperazine is a widely studied solvent for post‐combustion carbon dioxide capture. To investigate the possibilities of further improving this process, the electronic and steric effects of CH3, CH2F, CH2OH, CH2NH2, COCH3, and CN groups of 2,5‐disubstituted piperazines on the pKa and carbamate stability towards hydrolysis are investigated by quantum chemical methods. For the calculations, B3LYP, M11L, and spin‐component‐scaled MP2 (SCS‐MP2) methods are used and coupled with the SMD solvation model. The experimental pKa values of piperazine, 2‐methylpiperazine, and 2,5‐dimethylpiperazine agree well with the calculated values. The present study indicates that substitution of CH3, CH2NH2, and CH2OH groups on the 2‐ and 5‐positions of piperazine has a positive impact on the CO2 absorption capacity by reducing the carbamate stability towards hydrolysis. Furthermore, their higher boiling points, relative to piperazine itself, will lead to a reduction of volatility‐related losses.
Rapid and Cost‐Effective Synthesis of Nanosized Zeolitic Imidazolate Framework‐7 with N,N′‐Dimethylformamide as Solvent and Metal Acetate Salt as Metal Source
Authors: Wang Xiang , Huang Pengcheng , Yu Ping , Yang Lifen , Mao Lanqun
Published: April 2014

In this study, a new method was developed for the rapid and cost‐effective synthesis of nanosized zeolitic imidazolate framework‐7 (ZIF‐7) nanocrystals with a high yield and a low molar ratio of benzimidazole ligand to metal salt (2:1) by using N,N′‐dimethylformamide (DMF) as the solvent and zinc acetate dihydrate (Zn(OAc)2⋅2 H2O) as the metal source. The synthesized ZIF‐7 nanocrystals have a size of approximately 50–80 nm, and tend to aggregate or become intergrown to form irregular nanoparticles of about 200–300 nm in size. The morphology and yield of the ZIF‐7 nanocrystals can be tuned easily by changing the synthetic parameters such as the composition of the solvent and concentrations of reagents. The synthesized ZIF‐7 nanocrystals exhibit good thermal and chemical stability, CO2 capture capability, and fluorescent properties. Remarkably, we find that the synthetic strategy developed here can be extended to the syntheses of other kinds of ZIFs including ZIF‐69 and ZIF‐90. This study offers a new, simple synthetic strategy for the high‐yield preparation of ZIF materials.