bluuebunny/crossref_metadata_2025 huggingface dataset:
­Chemical profiling and biological activity of Peperomia blanda (Jacq.) Kunth
Authors: Al-Madhagi Wafa M. , Mohd Hashim Najihah , Awad Ali Nasser A. , Alhadi Abeer A. , Abdul Halim Siti Nadiah , Othman Rozana
Published: June 2018

Background

Peperomia belongs to the family of Piperaceae. It has different uses in folk medicine and contains rare compounds that have led to increased interest in this genus. Peperomia blanda (Jacq.) Kunth is used as an injury disinfectant by Yemeni people. In addition, the majority of Yemen’s population still depend on the traditional remedy for serious diseases such as cancer, inflammation and infection. Currently, there is a deficiency of scientific evidence with regards to the medicinal plants from Yemen. Therefore, this study was performed to assess the chemical profile and in vitro antioxidant and cytotoxic activities of P. blanda.

Methods

Chemical profiling of P. blanda was carried out using gas chromatography mass spectrometry (GCMS) followed by isolation of bioactive compounds by column chromatography. DPPH• and FRAP assays were used to evaluate antioxidant activity and the MTT assay was performed to estimate the cytotoxicity activity against three cancer cell lines, namely MCF-7, HL-60 and WEHI-3, and three normal cell lines, MCF10A, WRL-68 and HDFa.

Results

X-ray crystallographic data for peperomin A is reported for the first time here and N,N′-diphenethyloxamide was isolated for the first time from Peperomia blanda. Methanol and dichloromethane extracts showed high radical scavenging activity with an IC50 of 36.81 ± 0.09 µg/mL, followed by the dichloromethane extract at 61.78 ± 0.02 µg/mL, whereas the weak ferric reducing activity of P. blanda extracts ranging from 162.2 ± 0.80 to 381.5 ± 1.31 µg/mL were recorded. In addition, petroleum ether crude extract exhibited the highest cytotoxic activity against all the tested cancer cell lines with IC50 values of 9.54 ± 0.30, 4.30 ± 0.90 and 5.39 ± 0.34 µg/mL, respectively. Peperomin A and the isolated mixture of phytosterol (stigmasterol and β-sitosterol) exhibited cytotoxic activity against MCF-7 and WE-HI cell lines with an IC50 of (5.58 ± 0.47, 4.62 ± 0.03 µg/mL) and (8.94 ± 0.05, 9.84 ± 0.61 µg/mL), respectively, compared to a standard drug, taxol, that has IC50 values of 3.56 ± 0.34 and 1.90 ± 0.9 µg/mL, respectively.

Conclusion

The activities of P. blanda extracts and isolated compounds recorded in this study underlines the potential that makes this plant a valuable source for further study on anticancer and antioxidant activities.
A new predator connecting the abyssal with the hadal in the Kuril-Kamchatka Trench, NW Pacific
Authors: Lörz Anne-Nina , Jażdżewska Anna Maria , Brandt Angelika
Published: June 2018

The bathyal to hadal deep sea of north-west Pacific Ocean was recently intensively sampled during four international expeditions (KuramBio I and II, SoJaBio and SokhoBio). A large amphipod,Rhachotropis saskian. sp., was sampled in the Kuril-Kamchatka Trench and increases the number of described hadal species of that area to eight. A detailed description of the new species is provided, including illustrations, scanning-microscope images and molecular analysis. This predatory species was sampled at both continental and ocean abyssal margins of the Kuril-Kamchatka Trench as well as at hadal depths of the trench. The wide bathymetric distribution of the new species over more than 3,000 m is confirmed by molecular analysis, indicating that the Kuril Kamchatka Trench is not a distribution barrier for this species. However, the molecular analysis indicated the presence of isolation by distance of the populations of the studied taxon.
Force versus fury: Sex differences in the relationships among physical and psychological threat potential, the facial width‐to‐height ratio, and judgements of aggressiveness
Authors: MacDonell Elliott T. , Geniole Shawn N. , McCormick Cheryl M.
Published: June 2018

Individuals with larger facial width‐to‐height ratios (FWHRs) are judged as more threatening, and engage in more threat‐related behavior, than do individuals with smaller FWHRs. Here we identified components of threat potential that are related to the FWHR. In Study 1, the FWHR was correlated positively with physical threat potential (bicep size) in women and with both physical and psychological (anger proneness) threat potential in men. Behavioral aggression was measured in a subset of these participants using the Point Subtraction Aggression Paradigm (costly aggression) and a Money Allocation Task (non‐costly aggression). Psychological (but not physical) threat potential predicted non‐costly aggression and physical (but not psychological) threat potential predicted costly aggression. In Study 2, a separate set of participants judged the anger proneness, strength, or aggressiveness of male participants photographed in Study 1. Participants’ judgements of all three characteristics were associated with the FWHR, and there were sex differences in how aggressiveness was conceptualized (for women, aggressiveness was associated with anger proneness, for men, aggressiveness was associated with strength). These results are consistent with the hypothesis that the FWHR may be an adaptation to cue the threat potential of men.
Nanoparticles of Metal‐Organic Frameworks: On the Road to In Vivo Efficacy in Biomedicine
Authors: Simon‐Yarza Teresa , Mielcarek Angelika , Couvreur Patrick , Serre Christian
Published: June 2018

In the past few years, numerous studies have demonstrated the great potential of nano particles of metal‐organic frameworks (nanoMOFs) at the preclinical level for biomedical applications. Many of them were reported very recently based on their bioactive composition, anticancer application, or from a general drug delivery/theranostic perspective. In this review, the authors aim at providing a global view of the studies that evaluated MOFs' biomedical applications at the preclinical stage, when in vivo tests are described either for pharmacological applications or for toxicity evaluation. The authors first describe the current surface engineering approaches that are crucial to understand the in vivo behavior of the nanoMOFs. Finally, after a detailed and comprehensive analysis of the in vivo studies reported with MOFs so far, and considering the general evolution of the drug delivery science, the authors suggest new directions for future research in the use of nanoMOFs for biomedical applications.
Real‐Time Cellular Cytochrome C Monitoring through an Optical Microfiber: Enabled by a Silver‐Decorated Graphene Nanointerface
Authors: Li Hongtao , Huang Yunyun , Chen Chaoyan , Xiao Aoxiang , Hou Guanhua , Huang Yugang , Feng Xinhuan , Guan Bai‐Ou
Published: June 2018

The translocation of cytochrome c (cyt c) from mitochondria and out of cell is an important signal of cell apoptosis. Monitoring this process extracellularly without invasion and cytotoxicity to cells is of great importance to understand certain diseases at the cellular level; however, it requires sensors with ultrahigh sensitivity and miniature size. This study reports an optical microfiber aptasensor with a silver‐decorated graphene (Ag@RGO) nanointerface for real‐time cellular cyt c monitoring. Owing to an interfacial sensitization effect coupled with the plasmonic electromagnetic enhancement of silver nanoparticles and chemical enhancement of graphene platforms, which enhances the energy density on microfiber surface obviously, the lowest limit of detection achieved is 6.82 × 10−17m, which is approximately five orders of magnitude lower than those of existing methods. This microfiber successfully detects the ultralow concentrations of cyt c present during the initial stage of apoptosis in situ. As the microfiber functionalized by Ag@RGO nanointerface can be varied to meet any specific detection objective, this work opens up new opportunities to quantitatively monitor biological functions occurring at the cellular level.
Nahinfrarotaktive Bleichalkogenid‐Quantenpunkte: Herstellung, postsynthetischer Ligandenaustausch und Anwendungen in Solarzellen
Authors: Shrestha Aabhash , Batmunkh Munkhbayar , Tricoli Antonio , Qiao Shi Zhang , Dai Sheng
Published: June 2018

Quantenpunkte (QDs) von Bleichalkogeniden (z. B. PbS, PbSe und PbTe) sind nahinfrarotaktive Materialien, die großes Potenzial für einen breiten Bereich von Anwendungen wie Photovoltaik, Optoelektronik, Sensorik und Bioelektronik zeigen. Oberflächenliganden spielen eine wesentliche Rolle bei der Herstellung und postsynthetischen Modifizierung von QDs sowie bei deren Einsatz in Anwendungen. Daher ist ein gutes Verständnis des Einflusses von Oberflächenliganden auf die Synthese und Eigenschaften von QDs für deren Anwendungen in verschiedenen Bauelementen unerlässlich. Der vorliegende Aufsatz beschäftigt sich mit der Anwendung kolloidaler Synthesetechniken zur Herstellung von bleichalkogenidbasierten QDs. Der Schwerpunkt liegt auf dem Einfluss von Oberflächenliganden auf die QD‐Synthese sowie dem Ligandenaustausch in Lösung. Angesichts der Bedeutung von Bleichalkogenid‐QDs als möglichen Lichtsammlern richten wir unsere Aufmerksamkeit besonders auf die aktuellen Fortschritte von PV‐Anwendungen mit diesen QDs.
Organic‐Free Synthesis of Silicoaluminophosphate Molecular Sieves
Authors: Park Sung Hwan , Choi Wanuk , Choi Hyun June , Hong Suk Bong
Published: June 2018

Silicoaluminophosphate (SAPO) molecular sieves are an important class of microporous materials and are useful for industrial catalysis and separations. They have been synthesized exclusively by the use of expensive and environmentally unfriendly organic structure‐directing agents. Now the synthesis of SAPO molecular sieves is reported with MER, EDI, GIS, and ANA topologies under wholly inorganic conditions. Multinuclear MAS NMR analyses demonstrate the presence of Si, Al, and P atoms in their frameworks. These SAPO materials all have unusually high framework charge densities (0.25–0.46), owing to the small size of alkali metal cations used as an inorganic structure‐directing agent. A continuous Si increase in the synthesis gel for MER‐type SAPO molecular sieves led to the formation of framework Si(0Al) units, decreasing the number of extra‐framework cations per unit cell and thus making the resulting solid useful for CO2 adsorption.
Charge Separation in a Multifunctionalized Framework of Hydrogen‐Bonded Periodic Mesoporous Organosilica
Authors: Mizoshita Norihiro , Inagaki Shinji
Published: June 2018

Integration of functional molecular parts into nanoporous materials in a state that allows intermolecular charge or energy transfer is one of the key approaches to the development of photofunctional and electroactive materials. Herein, we report charge separation in a functionalized framework of a periodic mesoporous organosilica (PMO) self‐assembled by hydrogen bonds. Electroactive π‐conjugated organic species with different electron‐donating and electron‐accepting properties were selectively fixed onto the external surface of a nanoparticulate PMO, within the pore wall, and onto the surface of the internal mesopore. UV irradiation of the modified PMO resulted in photoinduced electron transfer and charge separation from the external surface to the pore wall and from the pore wall to the surface of the internal mesopores. These results suggest the high potential of multifunctionalized PMOs in the construction of photocatalytic reaction fields.
The Effects of a Short‐Radius Elbow on Electromagnetic Flowmeter Accuracy
Authors: Beck Kade J. , Weller Ryan P. , Barfuss Steven L. , Johnson Michael C.
Published: June 2018

This study was conducted to show the effects that a short‐radius elbow has on electromagnetic flowmeter accuracy. Previous laboratory studies have shown that non‐ideal piping affects the accuracy of electromagnetic flowmeters. The results of this study indicated that many of the meters tested did not meet their own manufacturer's specified accuracy either in straight pipe or with the required straight pipe installed upstream of the meter and downstream of a short‐radius elbow. However, nearly all meters in this study were repeatable to within ±0.55% when installed in straight pipe. The results illustrate that when a magnetic flowmeter is to be installed in either straight pipe or piping with upstream disturbances, a laboratory calibration will improve the installed accuracy of the meter.
Much ado about nothing: The zero effect in life‐saving decisions
Authors: Zhang Yufeng , Slovic Paul
Published: June 2018

Zero is a special value in our daily lives, and previous research on how zero values affect decision making leaves many questions to be explored. The present research examined the zero effect in life‐saving decisions and found that people expressed strong preferences for options offering a possibility that no one will die, even when the expected loss was relatively high. The prominence effect (the notion that the option with possibly zero deaths is easy to defend and justify) was proposed as one possible explanation. Furthermore, we also found that the zero effect in these life‐saving decisions occurs only in loss framing rather than gain framing. We discuss the relationships between the zero effect, framing, and evaluation mode in life saving and other domains.
Improved two‐stage group sequential procedures for testing a secondary endpoint after the primary endpoint achieves significance
Authors: Li Huiling , Wang Jianming , Luo Xiaolong , Grechko Janis , Jennison Christopher
Published: June 2018

In two‐stage group sequential trials with a primary and a secondary endpoint, the overall type I error rate for the primary endpoint is often controlled by an α‐level boundary, such as an O'Brien‐Fleming or Pocock boundary. Following a hierarchical testing sequence, the secondary endpoint is tested only if the primary endpoint achieves statistical significance either at an interim analysis or at the final analysis. To control the type I error rate for the secondary endpoint, this is tested using a Bonferroni procedure or any α‐level group sequential method. In comparison with marginal testing, there is an overall power loss for the test of the secondary endpoint since a claim of a positive result depends on the significance of the primary endpoint in the hierarchical testing sequence. We propose two group sequential testing procedures with improved secondary power: the improved Bonferroni procedure and the improved Pocock procedure. The proposed procedures use the correlation between the interim and final statistics for the secondary endpoint while applying graphical approaches to transfer the significance level from the primary endpoint to the secondary endpoint. The procedures control the familywise error rate (FWER) strongly by construction and this is confirmed via simulation. We also compare the proposed procedures with other commonly used group sequential procedures in terms of control of the FWER and the power of rejecting the secondary hypothesis. An example is provided to illustrate the procedures.
Extracellular Vesicles in Oncology: Progress and Pitfalls in the Methods of Isolation and Analysis
Authors: Lucchetti Donatella , Fattorossi Andrea , Sgambato Alessandro
Published: June 2018

The possibility to study solid tumors through the analysis of extracellular vesicles in biological fluids is one of the most exciting and rapidly advancing field in cancer research. The extracellular vesicles are tiny sacs released in both physiological and pathological conditions and can be used to monitor the evolution of several pathological states, including neoplastic diseases. Indeed, these vesicles carry biological informations and can affect the behavior of recipient cells by transferring proteins, DNA, RNA, and microRNA. In this review the authors analyze the methods to collect biological fluid samples (urine, plasma/serum, and cell supernatant), and to isolate and quantify extracellular vesicles highlighting advantages and drawbacks. Moreover, the authors provide an overview on the adoption and the advantages of the methods (such as digital PCR, next generation sequencing, reverse‐phase protein microarrays, flow‐cytometry, etc.) most frequently used to analyze the molecular content of extracellular vesicles. Despite the great scientific interest on this topic, there is still a great uncertainty about which is the best method for the collection, isolation, quantification, and molecular evaluation of these vesicles and a standardization is needed. The features of EVs make them ideal candidates for liquid biopsy‐based biomarkers. However, the small size of EVs makes their analysis very difficult and requires multiple advanced technologies, being therefore a limitation.
Rational design of thiolase substrate specificity for metabolic engineering applications
Authors: Bonk Brian M. , Tarasova Yekaterina , Hicks Michael A. , Tidor Bruce , Prather Kristala L. J.
Published: June 2018

Metabolic engineering efforts require enzymes that are both highly active and specific toward the synthesis of a desired output product to be commercially feasible. The 3‐hydroxyacid (3HA) pathway, also known as the reverse β‐oxidation or coenzyme‐A‐dependent chain‐elongation pathway, can allow for the synthesis of dozens of useful compounds of various chain lengths and functionalities. However, this pathway suffers from byproduct formation, which lowers the yields of the desired longer chain products, as well as increases downstream separation costs. The thiolase enzyme catalyzes the first reaction in this pathway, and its substrate specificity at each of its two catalytic steps sets the chain length and composition of the chemical scaffold upon which the other downstream enzymes act. However, there have been few attempts reported in the literature to rationally engineer thiolase substrate specificity. In this study, we present a model‐guided, rational design study of ordered substrate binding applied to two biosynthetic thiolases, with the goal of increasing the ratio of C6/C4 products formed by the 3HA pathway, 3‐hydroxy‐hexanoic acid and 3‐hydroxybutyric acid. We identify thiolase mutants that result in nearly 10‐fold increases in C6/C4 selectivity. Our findings can extend to other pathways that employ the thiolase for chain elongation, as well as expand our knowledge of sequence–structure–function relationship for this important class of enzymes.
Exposure to attachment narratives dynamically modulates cortical arousal during the resting state in the listener
Authors: Borchardt Viola , Surova Galina , van der Meer Johan , Bola Michał , Frommer Jörg , Leutritz Anna Linda , Sweeney‐Reed Catherine M. , Buchheim Anna , Strauß Bernhard , Nolte Tobias , Olbrich Sebastian , Walter Martin
Published: June 2018

Background

Affective stimulation entails changes in brain network patterns at rest, but it is unknown whether exogenous emotional stimulation has a prolonged effect on the temporal dynamics of endogenous cortical arousal. We therefore investigated differences in cortical arousal in the listener following stimulation with different attachment‐related narratives.

Methods

Resting‐state EEG was recorded from sixteen healthy subjects for ten minutes each with eyes closed: first at baseline and then after passively listening to three affective narratives from strangers about their early childhood experiences (prototypical for insecure‐dismissing, insecure‐preoccupied, and secure attachment). Using the VIGALL 2.1 algorithm, low or high vigilance stages in consecutive EEG segments were classified, and their dynamic profile was analyzed. Questionnaires assessed the listeners’ emotional response to the content of the narrative.

Results

As a general effect of preceding affective stimulation, vigilance following the stimulation was significantly elevated compared to baseline rest, and carryover effects in dynamic vigilance profiles were observed. A difference between narrative conditions was revealed for the insecure‐dismissing condition, in which the decrease in duration of high vigilance stages was fastest compared to the other two conditions. The behavioral data supported the observation that especially the insecure narratives induced a tendency in the listener to affectively disengage from the narrative content.

Discussion

This study revealed carryover effects in endogenous cortical arousal evoked by preceding affective stimulation and provides evidence for attachment‐specific dynamic alterations of brain states and individual differences in emotional reactivity.
Peptides Derived from Histone 3 and Modified at Position 18 Inhibit Histone Demethylase KDM6 Enzymes
Authors: Jones Sarah E. , Olsen Lars , Dorosz Jerzy , Seger Signe T. , Andersson Jan L. , Kristensen Line H. , Gajhede Michael
Published: June 2018

The KDM6 subfamily of histone lysine demethylases has recently been implicated as a putative target in the treatment of a number of diseases; this makes the availability of potent and selective inhibitors important. Due to high sequence similarity of the catalytic domain of Jumonji C histone demethylases, the development of small‐molecule, family‐specific inhibitors has, however, proven challenging. One approach to achieve the selective inhibition of these enzymes is the use of peptides derived from the substrate, the histone 3 C terminus. Here we used computational methods to optimize such inhibitors of the KDM6 family. Through natural amino acid substitution, it is shown that a K18I variant of a histone H3 derived peptide significantly increases affinity towards the KDM6 enzymes. The crystal structure of KDM6B in complex with a histone 3 derived K18I peptide reveals a tighter fit of the isoleucine side chain, compared with that of the arginine. As a consequence, the peptide R17 residue also has increased hydrophilic interactions. These interactions of the optimized peptide are likely to be responsible for the increased affinity to the KDM6 enzymes.
Granulomatous fasciitis followed by morphea profunda: Is granulomatous fasciitis part of a spectrum of deep morphea? A case report and review of the literature
Authors: Christensen Angie , Di Loreto Christina , Smitaman Edward , Paravar Taraneh , Jones Karra A. , Guma Monica
Published: June 2018

Key Clinical Message

Although eosinophilic fasciitis is known to be part of the deep morphea spectrum, this first report of the coexistence of granulomatous fasciitis and morphea profunda suggests that granulomatous fasciitis may also be a part of the spectrum of deep morphea.
Visceral leishmaniasis in acute myeloid leukemia revealed on peripheral blood smear
Authors: Moniot Maxime , Loyens Maxime , Mary Charles , L’Ollivier Coralie
Published: June 2018

Key Clinical Message

Images of parasitic forms of Leishmania infantum are typical in the hands of a skilled expert but should be known by biologists of Hematology Department. In an endemic region, the diagnosis of visceral leishmaniasis (VL) must be considered because of its potential role in accelerating hematological malignancy.
The Lived Experiences of Men in a Master's Counseling Program
Authors: Crockett Stephanie , Elghoroury Dena , Popiolek Melanie , Wummel Brian
Published: June 2018

Using phenomenological methodology, the authors explored the experiences of 11 men in a master's‐level counseling program. Participants described the challenges and advantages of being a minority in number, being in a relational environment, and having an awareness of a patriarchal system. These findings suggest the importance of counselor educator awareness of the unique barriers male students face.
Counselor Educator Mothers: A Quantitative Analysis of Job Satisfaction
Authors: Neale‐McFall Cheryl , Eckart Emeline , Hermann Mary , Haskins Natoya , Ziomek‐Daigle Jolie
Published: June 2018

The authors examined the occupational satisfaction of 107 counselor educator mothers and found that work‐to‐family enrichment, support from colleagues, and number of children under age 6 were significant predictors of occupational satisfaction. These results underscore the importance of policies and programs to increase occupational satisfaction of academic mothers and to support their recruitment and retention.
Materials Based on Antimony and Bismuth for Sodium Storage
Authors: Li Xinyan , Ni Jiangfeng , Savilov S. V. , Li Liang
Published: June 2018

Sodium‐ion batteries (SIBs) that efficiently store electricity into chemical energy have been extensively pursued because of their great potential for low‐cost and large‐scale stationary application such as smart grid and renewable energy. Successful deployment of SIBs requires efficient anode materials that could store Na+ ions via a reversible way at reasonable rates. Materials based on antimony and bismuth are capable of storing a high‐concentration of Na+ ions via a reversible alloying reaction at suitable redox potentials, and thus have drawn substantial attention. However, these electrode materials are facing significant technical challenges, such as poor conductivity, multiple phase transformation, and severe volume swelling and shrinking, which make efficient materials design a necessity. In this review, we will give a latest overview of research progress in the design and application of electrode materials based on antimony and bismuth, and offer some value insights into their future development in sodium storage.
Topology‐Selective, Fluorescent “Light‐Up” Probes for G‐Quadruplex DNA Based on Photoinduced Electron Transfer
Authors: Xie Xiao , Reznichenko Oksana , Chaput Ludovic , Martin Pascal , Teulade‐Fichou Marie‐Paule , Granzhan Anton
Published: June 2018

Six novel probes were prepared by covalent attachment of a G4‐DNA ligand (bis(quinolinium) pyridodicarboxamide; PDC) to various coumarin or pyrene fluorophores. In the absence of DNA, the fluorescence of all probes is quenched due to intramolecular photoinduced electron transfer (PET), as evidenced by photophysical and electrochemical studies, molecular modeling, and DFT calculations. All probes demonstrate similarly high thermal stabilization of various G4‐DNA substrates belonging to different folding topologies, as assessed by fluorescence melting experiments; however, their fluorimetric response is strongly heterogeneous with respect to the structures of the probes and G4‐DNA targets. Thus, the probes containing the 7‐diethylaminocoumarin fluorophore demonstrate significant fluorescence enhancement in the presence of G4‐DNA, with the strongest “light‐up” response (20‐ to 180‐fold) observed for antiparallel G4 structures as well as for hybrid G4 structures, formed by the variants of human telomeric sequence and capable of a conformation change to the antiparallel isoform. These results shed light on the influence of the linker and electronic properties of fluorophores on the efficiency of G4‐DNA “light‐up” probes operating via PET.
Making a Splash in Homogeneous CO2 Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms
Authors: Wiedner Eric S. , Linehan John C.
Published: June 2018

Molecular catalysts for hydrogenation of CO2 are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO2 hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO2. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO2. Additionally, the solvent can impact catalysis by converting CO2 into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems.
Au@TiO2 Core–Shell Composites for the Photocatalytic Reduction of CO2
Authors: Pougin Anna , Dodekatos Georgios , Dilla Martin , Tüysüz Harun , Strunk Jennifer
Published: June 2018

Au/TiO2 catalysts in different geometrical arrangements were designed to explore the role of morphology and structural properties for the photocatalytic reduction of CO2 with H2O in the gas‐phase. The most active sample was a Au@TiO2 core–shell catalyst with additional Au nanoparticles (NPs) deposited on the outer surface of the TiO2 shell. CH4 and CO are the primary carbon‐containing products. Large amounts of H2 are additionally formed by photocatalytic H2O splitting. Shell thickness plays a critical role. The highest yields were observed with the thickest layer of TiO2, stressing the importance of the semiconductor for the reaction. Commercial TiO2 with and without Au NPs was less active in the production of CH4 and CO. The enhanced activation of CO2 on the core–shell system is concluded to result from electronic interaction between the gold core, the titania shell, and the Au NPs on the outer surface. The improved exposure of Au−TiO2 interface contributes to the beneficial effect.
Atom‐ and Mass‐economical Continuous Flow Production of 3‐Chloropropionyl Chloride and its Subsequent Amidation
Authors: Movsisyan Marine , Heugebaert Thomas S. A. , Roman Bart I. , Dams Rudolf , Van Campenhout Rudy , Conradi Matthias , Stevens Christian V.
Published: June 2018

3‐Chloropropionyl chloride is a chemically versatile building block with applications in the field of adhesives, pharmaceuticals, herbicides and fungicides. Its current production entails problems concerning safety, prolonged reaction times and the use of excessive amounts of chlorinating reagents. We developed a continuous flow procedure for acid chloride formation from acrylic acid and a consecutive 1,4‐addition of hydrogen chloride generating 3‐chloropropionyl chloride, as presented in this paper. Up to 94 % conversion was reached in 25 minutes at mild temperatures and pressures. This continuous flow method offers a safer alternative and is highly efficient in terms of consumption of starting product and shorter residence time. Valorization of this building block is exemplified by the synthesis of beclamide, a compound with sedative and anticonvulsant properties. Over 80 % conversion towards this drug was achieved in 1 minute in a continuous flow setup. Further research is needed to telescope the synthesis of 3‐chloropropionyl chloride and subsequent beclamide formation without intermediate purification.
Slow Magnetic Relaxation in a Palladium–Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion
Authors: Izuogu David C. , Yoshida Takefumi , Zhang Haitao , Cosquer Goulven , Katoh Keiichi , Ogata Shuhei , Hasegawa Miki , Nojiri Hiroyuki , Damjanović Marko , Wernsdorfer Wolfgang , Uruga Tomoya , Ina Toshiaki , Breedlove Brian K. , Yamashita Masahiro
Published: June 2018

Invited for the cover of this issue are David C. Izuogu and Takefumi Yoshida with the group of Masahiro Yamashita and co‐workers at Tohoku University, Karlsruhe Institute of Technology, Aoyama Gakuin University, Japan Synchrotron Radiation Research Institute, Tohoku University Institute for Materials Research, University of Cambridge, University of Nigeria, Nsukka and National Institute for Materials Science. Read the full text of the article at 10.1002/chem.201800699.
Linear CuI2Pd0, CuIPd02, and AgI2Pd0 Metal Chains Supported by Rigid N,N′‐Diphosphanyl N‐Heterocyclic Carbene Ligands and Metallophilic Interactions
Authors: Ai Pengfei , Monakhov Kirill Yu. , van Leusen Jan , Kögerler Paul , Gourlaouen Christophe , Tromp Moniek , Welter Richard , Danopoulos Andreas A. , Braunstein Pierre
Published: June 2018

Invited for the cover of this issue is the group of Pierre Braunstein and Andreas Danopoulos at the University of Strasbourg. The image depicts the double short‐bite character of the two PCNHCP ligands. Read the full text of the article at 10.1002/chem.201801170.
The Direct and Indirect Effects of Self‐Efficacy on Salespeople's Emotional Exhaustion and Work‐Family Conflict: A Study Using the Job Demands‐Resources Model
Authors: Carballo‐Penela Adolfo , Varela José , Bande Belén
Published: June 2018

This study integrates Social Cognitive Theory with the Job Demands‐Resources Model to examine self‐efficacy in relation to emotional exhaustion and work‐family conflict (WFC) in a sample of 192 employees. The results obtained through structural equation analysis show: a negative association between self‐efficacy and both work overload and emotional exhaustion; a positive relationship between work overload and both emotional exhaustion and WFC; that work overload mediates the relation between self‐efficacy and both emotional exhaustion and WFC; that role ambiguity moderates the relation of self‐efficacy with work overload; and that tenure in the sales territory moderates the relation of work overload with WFC. Copyright © 2018 ASAC. Published by John Wiley & Sons, Ltd.
Denitrification Kinetics of High‐Strength Nitrate in Granular Sludge Reactors
Authors: Krishna Mohan Tulasi V. , Nancharaiah Yarlagadda V. , Venugopalan Vayalam P. , Satya Sai Pedapati M.
Published: June 2018

Biological denitrification of high‐strength nitrate is challenging due to building‐up of toxic nitrite to high levels. In this study, denitrification kinetics of high‐strength nitrate is investigated in a granular sludge reactor operated in sequencing batch mode. The nitrate concentrations are increased from 677, 1355, 2032, 2710, 3387, 4065–4742 mg L−1 NO3N in the reactor. Carbon and an electron source (acetate) are supplied at a fixed acetate‐carbon to nitrate‐nitrogen ratio of 1.5. At steady state, complete denitrification of 4742 mg L−1 NO3N in the feed is observed within the first 20 h of sequencing batch reactor (SBR) cycle. High denitrification rate constants are observed for NO3N concentrations from 677 to 2032 mg L−1. However, a decrease in denitrification rate constants is observed for nitrate‐N concentrations of 2710–4742 mg L−1, due to inhibition caused by transient accumulation of high levels of nitrite. Denitrifying biomass formed in the SBR is predominantly consisted of granular sludge, containing cocci, and rod‐shaped microorganisms. Cultivation of nitrite‐tolerant, denitrifying microbial community in granular sludge will help in the development of high rate reactors needed for process application.
Examining urban and rural differences in perceived timeliness of care among cancer patients: A SEER‐CAHPS study
Authors: Mollica Michelle A. , Weaver Kathryn E. , McNeel Timothy S. , Kent Erin E.
Published: June 2018

BACKGROUND

Rural cancer patients often have challenges in accessing quality care. This study examined associations between the place of residence at cancer diagnosis (urban vs rural) and patient ratings of access to care among older cancer survivors participating in Medicare‐managed care.

METHODS

Using Surveillance, Epidemiology, and End Results –Consumer Assessment of Healthcare Providers and Systems (SEER‐CAHPS) linked data, which included SEER data and Medicare CAHPS patient experience surveys, this study identified urban (n = 6140) and rural Medicare beneficiaries (n = 686) aged ≥ 65 years with a breast, lung, colorectal, or prostate cancer diagnosis who had completed a Medicare CAHPS survey between 1998 and 2013. Multivariable models examined associations between survivor residence at the time of diagnosis and CAHPS measures of timeliness and ease of getting care.

RESULTS

Respondents who resided in urban areas (vs rural) at the time of their cancer diagnosis rated their care significantly lower for Getting Care Quickly (b = −2.27; standard error = 0.95; P = .02). Although there were no overall significant differences for Getting Needed Care, there was a significant interaction between race/ethnicity and residence (P = .04): both non‐Hispanic black and Hispanic respondents residing in rural areas rated Getting Needed Care lower than those respondents residing in urban areas.

CONCLUSIONS

In contrast to prior studies, these findings suggest that rural survivors report more timely care than those in urban areas, but accessing needed care may be more challenging for racial/ethnic minority rural survivors. Future examination of specific barriers for urban and racial/ethnic minority rural survivors is warranted to ensure equitable access to quality cancer care. Cancer 2018. © 2018 American Cancer Society.
Glycocalyx Scaffolding to Control Cell Surface Glycan Displays
Authors: Huang Mia L. , Tota Ember M. , Verespy Stephen , Godula Kamil
Published: June 2018

This article describes a protocol for remodeling cells with synthetic glycoprotein and glycolipid mimetics that are functionalized with lipid anchors, allowing for cell surface display of specific glycan structures in predefined nanoscale arrangements. The complex chemical heterogeneity of glycans found on the cell surface or the glycocalyx renders analysis of the individual contributions of glycans difficult. This technique allows for the precise study of individual glycans at different regions of the glycocalyx, and may be useful for interrogating glycan interactions in infection or immunity or in stem cell differentiation. CHO‐Lec2 cells are prepared as adherent monolayers and, after reaching confluence, are incubated with the glycomaterials. Synthetic glycopolymers bearing α‐2,3‐sialyllactose glycans are used to decorate cellular surfaces in the form of 3D multivalent ligands projecting away from the cell surface, while α‐2,6‐sialyllactose glycolipid conjugates are used to anchor glycans in dynamic 2D arrays proximal to the cell membrane. Following washing, mimetic incorporation and glycan display can be analyzed using lectins with specificity for α‐2,3‐ or α‐2,6‐linked sialic acids. Flow cytometry data reveals that cell surface remodeling with either glycoconjugate mimetic occurs efficiently in a dose‐dependent manner. Combinations of glycoconjugates can also be employed simultaneously to generate a mixed glycocalyx with tunable composition and organization. © 2018 by John Wiley & Sons, Inc.
Measuring Histone Deacetylase Inhibition in the Brain
Authors: Reddy Doodipala Samba , Wu Xin , Golub Victoria M. , Dashwood W. Mohaiza , Dashwood Roderick H.
Published: June 2018

Histone deacetylases (HDACs) represent a family of enzymes that are targets for epigenetic modulation of genomic activity and may be beneficial in the treatment of many diseases, including cancer and central nervous system disorders. In animal models, HDAC inhibitors have neuroprotective, antiepileptogenic, and antidepressant effects. Assaying HDAC activity provides a robust method for identifying HDAC inhibitors and for assessing their effects under various physiological conditions or after pathological insults. In this unit, a simple and sensitive assay for measuring HDAC activity is described. HDAC activity in tissue lysates can be assessed fluorometrically using a Boc‐Lys(Ac) HDAC activity kit. HDACs catalyze the deacetylation of the substrate Boc‐Lys(Ac)‐AMC. Addition of a trypsin‐containing developer converts the deacetylated product to a quantifiable fluorophore that can be used both as a screening method to identify putative HDAC inhibitors and to assess the effects of these inhibitors on tissue and animal epigenetic‐modulated phenotypes. © 2018 by John Wiley & Sons, Inc.
A Detailed Study of Irradiation Requirements Towards an Efficient Photochemical Wohl‐Ziegler Procedure in Flow
Authors: Bonfield Holly E. , Williams Jason D. , Ooi Wei Xiang , Leach Stuart G. , Kerr William J. , Edwards Lee J.
Published: June 2018

A platform has been developed to enable standardization of light sources, allowing consistent scale‐up from high‐throughput screening in batch to flow, using the same pseudo‐monochromatic light source. The impact of wavelength and light intensity on a photochemical reaction was evaluated within this platform using the Wohl‐Ziegler benzylic bromination of 4‐methyl‐3‐(trifluoromethyl)benzonitrile with N‐bromosuccinimide as a model system. It was found that only 40 % of the maximum light intensity was required while still maintaining reaction rate, allowing more reliable temperature control and lower energy consumption. The optimized reaction conditions were subsequently applied to a range of synthetically relevant (hetero)aromatic compounds under continuous conditions, exploring the scope of the process within a mild and scalable procedure.
Neutral and functionally important genes shed light on phylogeography and the history of high‐altitude colonization in a widespread New World duck
Authors: Lozano‐Jaramillo Maria , McCracken Kevin G. , Cadena Carlos Daniel
Published: June 2018

Phylogeographic studies often infer historical demographic processes underlying species distributions based on patterns of neutral genetic variation, but spatial variation in functionally important genes can provide additional insights about biogeographic history allowing for inferences about the potential role of adaptation in geographic range evolution. Integrating data from neutral markers and genes involved in oxygen (O2)‐transport physiology, we test historical hypotheses about colonization and gene flow across low‐ and high‐altitude regions in the Ruddy Duck (Oxyura jamaicensis), a widely distributed species in the New World. Using multilocus analyses that for the first time include populations from the Colombian Andes, we also examined the hypothesis that Ruddy Duck populations from northern South America are of hybrid origin. We found that neutral and functional genes appear to have moved into the Colombian Andes from both North America and southern South America, and that high‐altitude Colombian populations do not exhibit evidence of adaptation to hypoxia in hemoglobin genes. Therefore, the biogeographic history of Ruddy Ducks is likely more complex than previously inferred. Our new data raise questions about the hypothesis that adaptation via natural selection to high‐altitude conditions through amino acid replacements in the hemoglobin protein allowed Ruddy Ducks to disperse south along the high Andes into southern South America. The existence of shared genetic variation with populations from both North America and southern South America as well as private alleles suggests that the Colombian population of Ruddy Ducks may be of old hybrid origin. This study illustrates the breadth of inferences one can make by combining data from nuclear and functionally important loci in phylogeography, and underscores the importance of complete range‐wide sampling to study species history in complex landscapes.
Murine macrophage chemokine receptor CCR2 plays a crucial role in macrophage recruitment and regulated inflammation in wound healing
Authors: Boniakowski Anna E. , Kimball Andrew S. , Joshi Amrita , Schaller Matt , Davis Frank M. , denDekker Aaron , Obi Andrea T , Moore Bethany B. , Kunkel Steve L. , Gallagher Katherine A.
Published: June 2018

Macrophages play a critical role in the establishment of a regulated inflammatory response following tissue injury. Following injury, CCR2+ monocytes are recruited from peripheral blood to wound tissue, and direct the initiation and resolution of inflammation that is essential for tissue repair. In pathologic states where chronic inflammation prevents healing, macrophages fail to transition to a reparative phenotype. Using a murine model of cutaneous wound healing, we found that CCR2‐deficient mice (CCR2−/−) demonstrate significantly impaired wound healing at all time points postinjury. Flow cytometry analysis of wounds from CCR2−/− and WT mice revealed a significant decrease in inflammatory, Ly6CHi recruited monocyte/macrophages in CCR2−/− wounds. We further show that wound macrophage inflammatory cytokine production is decreased in CCR2−/− wounds. Adoptive transfer of mT/mG monocyte/macrophages into CCR2+/+ and CCR2−/− mice demonstrated that labeled cells on days 2 and 4 traveled to wounds in both CCR2+/+ and CCR2−/− mice. Further, adoptive transfer of monocyte/macrophages from WT mice restored normal healing, likely through a restored inflammatory response in the CCR2‐deficient mice. Taken together, these data suggest that CCR2 plays a critical role in the recruitment and inflammatory response following injury, and that wound repair may be therapeutically manipulated through modulation of CCR2.
Association between levels of synovial anti‐citrullinated peptide antibodies and neutrophil response in patients with rheumatoid arthritis
Authors: Gorlino Carolina V. , Dave Mabel N. , Blas Rodrigo , Crespo María I. , Lavanchy Alicia , Tamashiro Héctor , Pardo‐Hildalgo Rodolfo , Pistoresi‐Palencia María C. , Di Genaro María S.
Published: June 2018

Rheumatoid arthritis (RA) is characterized by the presence of anti‐citrullinated peptide antibodies (ACPAs) and neutrophils infiltrating the synovial fluid (SF) of the affected joints. The aim of this work was to analyze whether the presence of ACPAs in SF is associated with neutrophil infiltration and with their phenotype in the inflamed joints of RA patients. We found that in the presence of ACPAs, the number of synovial neutrophils correlated with severe disease activity. The SF were divided according to synovial ACPA levels in negative‐ (<25 U/mL), low‐ (25–200 U/mL) and high level (˃200 U/mL; ACPAhigh). We observed that IL‐6, IL‐17, and IL‐8 were significantly elevated in ACPAhighSF and that IL‐8 levels correlated positively with neutrophil counts and with worse clinical manifestations. Additionally, in vitro incubation of neutrophils with ACPAhigh SF resulted in an increased ROS production and extracellular DNA release compared to neutrophils incubated with ACPA‐negative SF. These exacerbated effector functions were associated with a fraction of ICAM‐1‐positive neutrophils, which were induced by ACPAhigh SF. Likewise, in in vivo, we could also detect this subset among neutrophils present in ACPAhigh SF. In conclusion, the data presented here shed light on the role of SF‐ACPAs as inductors of a proinflammatory profile in neutrophils.
“Pigments of Life”, Molecules Well Suited to Investigate Metal–Ligand Symmetry‐Restricted Covalency
Authors: Casarin Maurizio , Carlotto Silvia
Published: June 2018

First principle quantum mechanical calculations are able to provide results comparable in accuracy to experimental measurements; moreover, it is unanimously recognized that the information they afford is often more accessible than that provided by conventional spectroscopy. Here we focus on the modelling and, possibly, on the prediction of X‐ray absorption spectroscopy (XAS) evidences at the L2,3‐edge of first row transition metal (M) macrocyclic complexes, which have been attracting an increasing interest because of their widespread technological applications. The comparison of homogeneous theoretical results with those achieved for complexes of the same central M ions but different ligands ultimately confirms the role played by the M chemical environment, the M electronic configuration and the M oxidation number in determining the appearance of L2,3 XAS features, which may be then exploited as a M fingerprint.
Conductive Inorganic–Organic Hybrid Layered Crystals Composed of Keggin‐Type Polyoxotungstates and a Heterocyclic Surfactant
Authors: Otobe Saki , Kiyota Yoshiki , Magira Shotaro , Misawa Toshiyuki , Fujio Katsuhiko , Naruke Haruo , Uchida Sayaka , Ito Takeru
Published: June 2018

Keggin‐type polyoxotungstate hybrid layered crystals are successfully synthesized in a single phase by using a heterocyclic surfactant. Heteropolyoxotungstate anions of [XW12O40]n– (XW12, X = P, Si; n = 3, 4) are hybridized with the dodecylpyridazinium (C12pda) cation. Single‐crystal X‐ray diffraction analyses reveal that all of the countercations of XW12 are replaced by C12pda cations. The layered structures consist of XW12 inorganic layers and C12pda organic layers, stacked alternately. In the PW12 hybrid crystal (1), the PW12 anions form a bilayer structure, comprising a one‐dimensional infinite chain of PW12 connected through short contacts. The SiW12 hybrid crystal (2) contains SiW12 monolayers isolated by heterocyclic moieties of the C12pda cations. The conductivity of 1, under an anhydrous atmosphere, is estimated to be 2.5 × 10–8 S cm–1 at 373 K, while the hybrid crystal 2 exhibits a maximum conductivity of 1.1 × 10–4 S cm–1 at 453 K.