bluuebunny/crossref_metadata_2025 huggingface dataset:
Spectroscopic models for the characterization of energetic particle beams in tokamak edge plasmas
Authors: Meireni Mutia , Hannachi Ibtissem , Rosato Joël , Marandet Yannick , Stamm Roland
Published: March 2018

We examine the possibility for a diagnostic of energetic particle beams based on passive spectroscopy, with a focus on the atomic lines observed in the edge region of tokamaks. Our investigation employs a quasi‐linear model for the collective electric field generated by the plasma‐beam instability. If the beam is sufficiently energetic, the electric field can be comparable to the thermal Holtsmark microfield, and the corresponding Stark effect on atomic energy levels can be observable on spectra. We investigate this issue and perform new hydrogen line shape calculations. The applicability of the model to the diagnostics of runaway electrons is discussed.
Electron acceleration in a homogeneous plasma by Bessel‐Gaussian and Gaussian pulses
Authors: Fallah R. , Khorashadizadeh S.M.
Published: March 2018

The process of electron acceleration by both Bessel‐Gaussian (BG) and Gaussian (G) laser pulses has been investigated comparatively in a homogeneous plasma. Starting with the hydrodynamics fluid and the Maxwell's equations, the three corresponding equations could be acquired which allow us to evaluate electron density perturbations (), wakefield (Ew) and electron energy‐gain (ΔW) respectively for both pulses. Here, the pulse duration and the electron plasma period are taken the same, and by utilizing the perturbation theory the proposed equations have been solved. The analytical results show that the wakefield which leads to electron acceleration, depends on pulse intensity (I), pulse length (L), pulse wavelength (λ) and plasma density (n). Furthermore, by comparing the outcomes, the BG pulse is found to be most suitable for wakefield excitation. The pertinent electron could be accelerated up to 90 MeV if I = 4 × 1021W/m2, L = 20 µm and n = 5.318 × 1024 m−3. Our results are in a good agreement with experimental data reported in literature.
Breather structures in a plasma with warm ions and Cairns electrons
Authors: Shan Shaukat Ali
Published: March 2018

The modulational instability (MI) of ion‐acoustic waves (IAWs) in a two‐component non‐Maxwellian hot plasma with Cairns distributed electrons is investigated. Using the derivative expansion method, a non‐linear Schrödinger equation (NLSE) is obtained. The criterion for MI, which occurs for small values of the carrier wavenumber, is obtained. It is found that non‐thermal parameter α modifies the criteria for MI instability. The analytical solutions of NLSE in the form of various types of freak waves, including the Peregrine soliton, the Akhmediev breather, and the Kuznetsov–Ma breather, are examined. The effects of the non‐thermal parameter as well as ion‐to‐electron temperature ratio on the rogue wave profile are discussed. Our results should be relevant to wave propagation stability. Non‐thermal models may play an increasingly important role in predicting complex plasma behaviour and understanding the underlying physical processes.
Urinary tract blastomycosis diagnosed by urine cytology
Authors: Vahidi Shifteh , Beckman Amy , Albrecht Kellen , Arbefeville Sophie , Ferrieri Patricia , Amin Khalid
Published: March 2018

Urinary tract blastomycosis is an uncommon manifestation of disseminated Blastomyces infection. Here, we report a 50‐year‐old male with common variable immunodeficiency who presented with urinary symptoms and a renal mass concerning for a kidney neoplasm. Urine cytology revealed typical broad‐based budding yeasts with thick‐walled refractile capsules, leading to diagnosis of urinary tract blastomycosis. In this case, urine cultures were negative, and urine cytology was the main method of diagnosis of blastomycosis. Thus, urine cytology represents a rapid and reliable method of diagnosing blastomycosis, which in the current case led to prompt treatment of this potentially life threatening infection.
Human papillomavirus detection with genotyping by the cobas and Aptima assays: Significant differences in HPV 16 detection?
Authors: Chorny Joseph A. , Frye Teresa C. , Fisher Beth L. , Remmers Carol L.
Published: March 2018

Background

The primary high‐risk human papillomavirus (hrHPV) assays in the United States are the cobas (Roche) and the Aptima (Hologic). The cobas assay detects hrHPV by DNA analysis while the Aptima detects messenger RNA (mRNA) oncogenic transcripts. As the Aptima assay identifies oncogenic expression, it should have a lower rate of hrHPV and genotype detection.

Methods

The Kaiser Permanente Regional Reference Laboratory in Denver, Colorado changed its hrHPV assay from the cobas to the Aptima assay. The rates of hrHPV detection and genotyping were compared over successive six‐month periods.

Results

The overall hrHPV detection rates by the two platforms were similar (9.5% versus 9.1%) and not statistically different. For genotyping, the HPV 16 rate by the cobas was 1.6% and by the Aptima it was 1.1%. These differences were statistically different with the Aptima detecting nearly one‐third less HPV 16 infections. With the HPV 18 and HPV 18/45, there was a slightly higher detection rate of HPV 18/45 by the Aptima platform (0.5% versus 0.9%) and this was statistically significant.

Conclusion

While HPV 16 represents a low percentage of hrHPV infections, it was detected significantly less by the Aptima assay compared to the cobas assay. This has been previously reported, although not highlighted. Given the test methodologies, one would expect the Aptima to detect less HPV 16. This difference appears to be mainly due to a significantly increased number of non‐oncogenic HPV 16 infections detected by the cobas test as there were no differences in HPV 16 detection rates in the high‐grade squamous intraepithelial lesions indicating that the two tests have similar sensitivities for oncogenic HPV 16.
A case of endocervical minimal deviation adenocarcinoma with varicolored cytopathologic features on Pap smear
Authors: Omori Makiko , Kondo Tetsuo , Nakazawa Kumiko , Shinohara Satoshi , Watanabe Yumika , Fukasawa Hiroko , Nakazawa Tadao , Hashi Akihiko , Hirata Shuji
Published: March 2018

We report a case of minimal deviation adenocarcinoma (MDA) of the uterine cervix showing varicolored cytopathologic features on Papanicolaou (Pap) smear, which may indicate features suggestive of lobular endocervical glandular hyperplasia (LEGH)‐adenocarcinoma sequence. A 57‐year‐old woman presented with a profuse amount of watery vaginal discharge. Gynecological examination revealed a cervical mass with involvement of the right parametrium. Conventional Pap smear showed hypercellularity consisting of approximately 4 types of clusters as follows: (1) clusters showing a monolayered honeycomb sheet of endocervical cells with golden‐yellow mucin and bland nuclei, (2) three‐dimensional clusters showing varicolored mucin and irregular nuclear overlapping, (3) irregularly shaped clusters showing distorted chicken‐wire‐mesh appearance with noticeable protrusions of the nuclei and clear or faint varicolored cytoplasm, and (4) crowded clusters showing scarce mucin and nuclear atypia. The surgically resected uterus revealed LEGH‐mimicking lesion with fused papillae and a cribriform pattern in the endocervix and many glands exhibiting gastric differentiation that invaded deeper areas of the stroma with a subtle stromal reaction. Compared with histologic findings, two types of clusters, the crowded cluster with scarce mucin and the cluster with distorted chicken‐wire‐mesh‐type appearance, were considered as adenocarcinoma, and the latter was interpreted as a gastric‐type adenocarcinoma. Three‐dimensional varicolored type clusters showed atypical features, but insufficient atypical features compared with those of adenocarcinoma. Detection of clusters with varicolored mucin on conventional Pap smear may provide a clue for the early recognition of the malignant potential of LEGH on cytology. The chicken‐wire‐mesh type clusters may be a characteristic cytologic finding of MDA.
Potential amelioration of nicotine‐induced toxicity by nanocurcumin
Authors: Chattopadhyay Krishna , Samanta Anwesha , Mukhopadhyay Subrata , Chattopadhyay Brajadulal
Published: March 2018

Clinical Research

Curcumin, a nontoxic bioactive agent of turmeric significantly reduces nicotine‐induced toxicity both at cellular and genetic levels. The clinical implication of native curcumin is hindered in the target cells due to its low aqueous solubility, poor bioavailability and poor pharmacokinetics. The problem was tried to overcome by preparing nanocurcumin with a view to improve its aqueous solubility and better therapeutic efficacy against nicotine‐induced toxicity. The prepared nanocurcumin was characterized by Ultraviolet‐visible spectroscopy; Field emission scanning electron microscopy (FE‐SEM); X‐ray diffraction (XRD); and Fourier transform infrared spectroscopy (FTIR). Female albino rats of Wistar strain were daily exposed to effective dose of nicotine (2.5 mg/kg, injected subcutaneously) and supplemented with effective dose of curcumin (80 mg/kg body weight orally) or nanocurcumin (4 mg/kg body weight orally) for 21 days. The preventive efficacies of curcumin and nanocurcumin were evaluated against the changes in liver function enzymes, kidney function parameters, lipid profiles, lipid‐peroxidation, anti‐oxidant status, and tissues damages etc. Results revealed that nanocurcumin more effectively ameliorated the nicotine‐induced toxicities at much lower concentration due to its higher aqueous solubility and more bioavailability. The nanocurcumin can be used as a potential therapeutic agent for better efficacy against nicotine‐induced toxicities than native curcumin.
Risk of dipeptidyl peptidase‐4 (DPP‐4) inhibitors on site‐specific cancer: A systematic review and meta‐analysis
Authors: Overbeek Jetty A. , Bakker Marina , van der Heijden Amber A.W.A. , van Herk‐Sukel Myrthe P.P. , Herings Ron M.C. , Nijpels Giel
Published: March 2018

The long‐term impact of dipeptidyl peptidase‐4 (DPP‐4) inhibition is unknown, and there are concerns about the influence of DPP‐4 inhibition on carcinogenesis of the pancreas and thyroid. As DPP‐4 is a rather unselective enzyme present in many tissues, we focused on all specific cancer types. PubMed and EMBASE were searched between January 2005 and April 2017 to identify studies comparing DPP‐4 inhibitors with either placebo or active drugs on cancer risk. Studies were included if they reported on at least one specific cancer outcome and had a follow‐up of at least 1 year after start of drug use. Methodological quality of the studies was assessed by the Cochrane Collaboration's tool and the Newcastle‐Ottawa Scale. Twenty‐five studies met the inclusion criteria (12 randomized controlled trials and 13 observational studies). Sample sizes of the DPP‐4 inhibitor groups ranged from 29 to 8212 patients for randomized controlled trials and from 2422 to 71 137 patients for observational studies. Mean age ranged from 51 to 76 years, and mean follow‐up was 1.5 years. None of the pooled (sensitivity) analyses, except the observational studies studying breast cancer (hazard ratio [95% CI]: 0.76 [0.60‐0.96]), showed evidence for an association between DPP‐4 inhibitors and site‐specific cancer. Also for pancreatic and thyroid cancer, no statistically significant risk was found. Based on the current literature, it is not possible to conclude whether DPP‐4 inhibitors were associated with an increased risk of site‐specific cancer. Future studies should address the methodological limitations and follow patients for a longer period to determine the long‐term cancer risk of DPP‐4 inhibitors.
The modality and redundancy effects in multimedia learning in children with dyslexia
Authors: Knoop‐van Campen Carolien A. N. , Segers Eliane , Verhoeven Ludo
Published: March 2018

The present study aimed to examine the modality and redundancy effects in multimedia learning in children with dyslexia in order to find out whether their learning benefits from written and/or spoken text with pictures. We compared study time and knowledge gain in 26 11‐year‐old children with dyslexia and 38 typically reading peers in a within‐subjects design. All children were presented with a series of user‐paced multimedia lessons in 3 conditions: pictorial information presented with (a) written text, (b) audio, or (c) combined text and audio. We also examined whether children's learning outcomes were related to their working memory. With respect to study time, we found modality and reversed redundancy effects. Children with dyslexia spent more time learning in the text condition, compared with the audio condition and the combined text‐and‐audio condition. Regarding knowledge gain, no modality or redundancy effects were evidenced. Although the groups differed on working memory, it did not influence the modality or redundancy effect on study time or knowledge gain. In multimedia learning, it thus is more efficient to provide children with dyslexia with audio or with auditory support.
Accounting for disturbance history in models: using remote sensing to constrain carbon and nitrogen pool spin‐up
Authors: Hanan Erin J. , Tague Christina , Choate Janet , Liu Mingliang , Kolden Crystal , Adam Jennifer
Published: March 2018

Disturbances such as wildfire, insect outbreaks, and forest clearing, play an important role in regulating carbon, nitrogen, and hydrologic fluxes in terrestrial watersheds. Evaluating how watersheds respond to disturbance requires understanding mechanisms that interact over multiple spatial and temporal scales. Simulation modeling is a powerful tool for bridging these scales; however, model projections are limited by uncertainties in the initial state of plant carbon and nitrogen stores. Watershed models typically use one of two methods to initialize these stores: spin‐up to steady state or remote sensing with allometric relationships. Spin‐up involves running a model until vegetation reaches equilibrium based on climate. This approach assumes that vegetation across the watershed has reached maturity and is of uniform age, which fails to account for landscape heterogeneity and non‐steady‐state conditions. By contrast, remote sensing, can provide data for initializing such conditions. However, methods for assimilating remote sensing into model simulations can also be problematic. They often rely on empirical allometric relationships between a single vegetation variable and modeled carbon and nitrogen stores. Because allometric relationships are species‐ and region‐specific, they do not account for the effects of local resource limitation, which can influence carbon allocation (to leaves, stems, roots, etc.). To address this problem, we developed a new initialization approach using the catchment‐scale ecohydrologic model RHESSys. The new approach merges the mechanistic stability of spin‐up with the spatial fidelity of remote sensing. It uses remote sensing to define spatially explicit targets for one or several vegetation state variables, such as leaf area index, across a watershed. The model then simulates the growth of carbon and nitrogen stores until the defined targets are met for all locations. We evaluated this approach in a mixed pine‐dominated watershed in central Idaho, and a chaparral‐dominated watershed in southern California. In the pine‐dominated watershed, model estimates of carbon, nitrogen, and water fluxes varied among methods, while the target‐driven method increased correspondence between observed and modeled streamflow. In the chaparral watershed, where vegetation was more homogeneously aged, there were no major differences among methods. Thus, in heterogeneous, disturbance‐prone watersheds, the target‐driven approach shows potential for improving biogeochemical projections.
Minor contribution of overstorey transpiration to landscape evapotranspiration in boreal permafrost peatlands
Authors: Warren Rebecca K. , Pappas Christoforos , Helbig Manuel , Chasmer Laura E. , Berg Aaron A. , Baltzer Jennifer L. , Quinton William L. , Sonnentag Oliver
Published: March 2018

Evapotranspiration (ET) is a key component of the water cycle, whereby accurate partitioning of ET into evaporation and transpiration provides important information about the intrinsically coupled carbon, water, and energy fluxes. Currently, global estimates of partitioned evaporative and transpiration fluxes remain highly uncertain, especially for high‐latitude ecosystems where measurements are scarce. Forested peat plateaus underlain by permafrost and surrounded by permafrost‐free wetlands characterize approximately 60% (7.0 × 107 km2) of Canadian peatlands. In this study, 22 Picea mariana (black spruce) individuals, the most common tree species of the North American boreal forest, were instrumented with sap flow sensors within the footprint of an eddy covariance tower measuring ET from a forest–wetland mosaic landscape. Sap flux density (JS), together with remote sensing data and in situ measurements of canopy structure, was used to upscale tree‐level JS to overstorey transpiration (TBS). Black spruce trees growing in nutrient‐poor permafrost peat soils were found to have lower mean JS than those growing in mineral soils. Overall, TBS contributed less than 1% to landscape ET. Climate‐change‐induced forest loss and the expansion of wetlands may further minimize the contributions of TBS to ET and increase the contribution of standing water.
Long‐term prognosis, subsequent pregnancy, contraception and overall management of peripartum cardiomyopathy: practical guidance paper from the Heart Failure Association of the European Society of Cardiology Study Group on Peripartum Cardiomyopathy
Authors: Sliwa Karen , Petrie Mark C. , Hilfiker‐Kleiner Denise , Mebazaa Alexandre , Jackson Alice , Johnson Mark R. , van der Meer Peter , Mbakwem Amam , Bauersachs Johann
Published: March 2018

Peripartum cardiomyopathy is an idiopathic cardiomyopathy presenting with heart failure secondary to left ventricular systolic dysfunction towards the end of pregnancy or in the months following delivery, where no other cause for heart failure is identified. Outcome varies from full recovery to residual left ventricular systolic dysfunction and even death. Many women return to their physician to acquire information on their long‐term prognosis, to seek medical advice regarding contraception, or when planning a subsequent pregnancy. This position paper summarizes current evidence for long‐term outcome, risk stratification of further pregnancies and overall management. Based on the best available evidence, as well as the clinical experience of the European Society of Cardiology Study Group on Peripartum Cardiomyopathy members, a consensus on pre‐ and postpartum management algorithms for women undergoing a subsequent pregnancy is presented.
Chloroquine‐treated dendritic cells require STAT1 signaling for their tolerogenic activity
Authors: Thome Rodolfo , Bonfanti Amanda Pires , Rasouli Javad , Mari Elisabeth Rose , Zhang Guang‐Xian , Rostami Abdolmohamad , Verinaud Liana
Published: March 2018

MS and EAE are T cell‐driven autoimmune diseases of the CNS where IL‐17‐producing Th17 cells promote damage and are pathogenic. Conversely, tolerogenic DCs induce Treg cells and suppress Th17 cells. Chloroquine (CQ) suppresses EAE through the modulation of DCs by unknown mechanisms. Here, we show that STAT 1 is necessary for CQ‐induced tolerogenic DCs (tolDCs) to efficiently suppress EAE. We observed that CQ induces phosphorylation of STAT1 in DCs in vivo and in vitro. Genetic blockage of STAT1 abrogated the suppressive activity of CQ‐treated DCs. Opposed to its WT counterparts, CQ‐treated STAT1−/− BMDCs were unable to suppress Th17 cells and increased EAE severity. Our findings show that STAT1 is a major signaling pathway in CQ‐induced tolDCs and may shed light on new therapeutic avenues for the induction of tolDCs in autoimmune diseases such as MS.
Synthesis and Characterization of Stable Gold(III) PNP Pincer Complexes
Authors: Grajeda Javier , Nova Ainara , Balcells David , Bruch Quinton J. , Wragg David S. , Heyn Richard H. , Miller Alexander J. M. , Tilset Mats
Published: March 2018

The first mononuclear AuIII PNP pincer complexes [PNP = bis(2‐diisopropylphosphinophenyl)amide] are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate‐bound complex [(PNP)Au(OAcF)][OAcF]. Both complexes were characterized by NMR spectroscopy and X‐ray crystallography. Electronic absorption spectroscopy and TD‐DFT studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The AuIII trifluoroacetate complex is surprisingly stable, and no alkene insertion was observed under ethylene (C2H4), even under high pressures and at high temperatures. DFT calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic C2H4‐bound intermediate invoked in a formal insertion reaction.
Synthesis and Reactivity of Copper(I) Complexes Based on C3‐Symmetric Tripodal HTIM(PR2)3 Ligands
Authors: Smirnova Ekaterina S. , Acuña‐Parés Ferran , Escudero‐Adán Eduardo C. , Jelsch Christian , Lloret‐Fillol Julio
Published: March 2018

We present the first example of non‐classical hydrogen bonding in CuI complexes. To this end, we have studied the coordination capacity of the tripodal phosphine ligands HTIM(PR2)3 {tris[1‐(di‐R‐phosphanyl)‐3‐methyl‐1H‐indol‐2‐yl]methane, R = Ph, iPr} towards copper, leading to a series of eight CuI complexes [{HTIM(PR2)3}CuX] [R = Ph (1–4), iPr (5–8); X = Cl–, I–, OTf–, BF4–]. An anagostic interaction in the CuI complexes has been proposed based on the results of 1H NMR, ultrahigh‐resolution X‐ray diffraction, and theoretical [atoms‐in‐molecules (AIM) and natural bonding orbital (NBO)] analyses of the electron density. Among the different synthesized complexes, [{HTIM(PPh2)3}CuOTf] (2) shows the strongest Cu···H–C interaction with a linear geometry (179.98°) and the shortest distance described so far [d(Cu–H) = 1.9 Å] in its toluene solvated form. Both parameters are characteristic of 3c–4e– interactions. In addition, we have found that these tripodal ligands exhibit unprecedented selectivity towards CuI ions. The synthesized HTIM(PR2)3CuI complexes have been found to be catalytically active and selective for the hydroboration of CO2 to formic acid.
Synthesis, Structure, and Electrochemical Properties of O‐Alkyldithiophosphato Nickel Complexes with Chelating Aminodiphosphine Ligands
Authors: Deng Chenglong , Wang Zheng , Xie Ying , He Jiao , Wei Juan , Zou Like , Xie Bin , Jiang Jin , Wu Yu , Ma Zhongyi , Hu Mengyuan , Li Yulong , Zhao Peihua , Liu Xufeng
Published: March 2018

Eight new O‐alkyldithiophosphato nickel complexes 1–8 with chelating aminodiphosphine ligands have been successfully synthesized in moderate yields by the treatment of O,O′‐alkydithiophosphoric acid salts (R1O)2P{S}SH·Et2NH (R1 = CH3, CH2CH3) with nickel aminodiphosphine precursors Ni[(Ph2P)2NR2]Cl2 [R2 = (CH2)3OCH3, (CH2)3SCH3, (CH2)2CH(CH3)2, CH(CH3)C6H5] in the presence of Et3N at room temperature. Meanwhile, reactions of Ni(S2P{OR1}2)2 and aminodiphosphine ligands (Ph2P)2NR2 in CHCl3 solvents at room temperature also resulted in the formation of the target complexes 1–8 in satisfactory yields. The two synthetic routes are found to be efficient pathways to prepare O‐alkyldithiophosphato nickel complexes with chelating aminodiphosphine ligands. All the new complexes were fully characterized by elemental analysis, FTIR and NMR (1H, 13C, 31P) spectroscopy, and particularly for three of them by X‐ray crystallography. Moreover, these complexes were found to be catalysts for hydrogen production in the presence of a weak acid under electrochemical conditions.
Mechanistic Considerations on Homogeneously Catalyzed Formic Acid Dehydrogenation
Authors: Iglesias Manuel , Oro Luis A.
Published: March 2018

The dehydrogenation of formic acid permits the production of hydrogen virtually free of carbon monoxide, which is a key requisite for its use in fuel cells. Moreover, HCOOH is a suitable hydrogen carrier, better in several crucial characteristics than other liquid organic hydrogen carriers, namely, low toxicity, high hydrogen content and recyclability (via CO2 hydrogenation). The most successfully employed catalysts are those based on Ir, Ru, Rh, and Fe metal centers. The catalytic cycles through which homogeneous metal complexes operate show a wide mechanistic diversity. The nature of catalytic cycle depends mainly on the nuclearity of the active species, the type of CO2 formation step (β‐hydride elimination, hydride abstraction, or outer‐sphere mechanism), and whether the rate‐limiting step relates to CO2 or H2 formation. Different outer‐sphere interactions have been proposed in the literature in order to explain the success of homogeneous catalyst, which seems to be common ground for most of the catalysts so far reported.
Tetranuclear Strontium and Barium Siloxide/Amide Clusters in Metal‐Ligand Cooperative Catalysis
Authors: Freitag Benjamin , Stegner Phillip , Thum Katharina , Fischer Christian A. , Harder Sjoerd
Published: March 2018

One‐pot reaction of 2,6‐iPr2‐aniline (DIPP‐NH2) with (Me2SiO)3 and Sr[N(SiMe3)2]2 (SrN′′2) gave a tetranuclear cluster consisting of four dianions [OSiMe2N‐DIPP]2– and four Sr2+ ions solvated each by one THF ligand. The general applicability of this method was investigated by variation of amine and metal. Anilines with smaller substituents led to insoluble uncharacterized coordination polymers, whereas bulkier anilines gave soluble product mixtures that could not be purified. Primary alkylamines neither led to isolable products. Introduction of a tBu group in para‐position of DIPP‐NH2, however, gave an isostructural cluster with increased solubility. Similar clusters could be obtained with barium. Both, the Sr and Ba clusters, were found to be active catalysts for a wide range of transformations: intramolecular alkene hydroamination, alkene hydrophoshination, pyridine hydroboration, pyridine hydrosilylation, and alkene hydrosilylation. The Ba catalysts were generally more active than the Sr catalysts. The tBu‐substituent in para‐position also had an accelerating effect, which is likely due to improved solubility.
Thermosensitive Seven‐Coordinate TbIII Complexes with LLCT Transitions
Authors: Ferreira da Rosa Pedro Paulo , Nakanishi Takayuki , Kitagawa Yuichi , Seki Tomohiro , Ito Hajime , Fushimi Koji , Hasegawa Yasuchika
Published: March 2018

Seven‐coordinate TbIII complexes with strong luminescence and thermosensing properties are reported. Mononuclear [Tb(tmh)3(PEB)] [tmh: 2,2,6,6‐tetramethyl‐3,5‐heptanedione, PEB: (diphenylphosphoryl)ethynyl]benzene and dinuclear [Tb2(tmh)6(m‐BPEB)] [m‐BPEB: 1,3‐bis(diphenylphosphoryl)ethynyl]benzene were characterized by single‐crystal X‐ray analysis. The quantum yields of [Tb(tmh)3(PEB)] and [Tb2(tmh)6(m‐BPEB)] were estimated to be 71 and 39 %, respectively. Thermosensing properties are evaluated by temperature‐dependent emission lifetime measurements (Arrhenius analysis), which are affected by the presence of ligand‐to‐ligand charge transfer (LLCT) bands. The LLCT bands are confirmed by DFT calculations.
Reactivity of a (Benzene)Ruthenium(II) Cation on a Di‐lacunary γ‐Keggin‐Type Silicotungstate and Synthesis of a Mono‐(Benzene)Ruthenium(II)‐Attached γ‐Keggin‐Type Silicotungstate
Authors: Kikuchi Masaya , Ota Hiromi , López Xavier , Nakaya Toshimi , Tsunoji Nao , Sano Tsuneji , Sadakane Masahiro
Published: March 2018

Invited for the cover of this issue is Masahiro Sadakane from Hiroshima University, Japan, collaborating with groups from Okayama University, Japan, and Universitat Rovira i Virgili, Spain. The cover image shows a new Ru‐containing‐heteropolytungstate.
DHA‐Enriched Phosphatidylcholine and DHA‐Enriched Phosphatidylserine Improve Age‐Related Lipid Metabolic Disorder through Different Metabolism in the Senescence‐Accelerated Mouse
Authors: Ding Lin , Zhang Tiantian , Che Hongxia , Zhang Lingyu , Xue Changhu , Chang Yaoguang , Wang Yuming
Published: March 2018

Aging is an independent risk factor for the development of atherosclerosis, which is characterized by hyperlipemia. The senescence‐accelerated mouse (SAMP8) is an animal model used in studies of aging, which is associated with a shift of fatty metabolism toward lipogenesis. This study investigates the effects of docosahexaenoic acid‐enriched phosphatidylcholine (DHA‐PC) and docosahexaenoic acid‐enriched phosphatidylserine (DHA‐PS) on age‐related lipid metabolic disorder in SAMP8 mice. Main findings and results: Both dietary DHA‐PC and DHA‐PS significantly decrease serum and hepatic lipid levels. The levels of DHA in hepatic total lipid are significantly increased in both DHA‐PC and DHA‐PS groups (2.59‐ and 2.33‐fold, respectively). Notably, supplementary DHA‐PS remarkably alters the ratio of PE to PC in liver. Mechanistically, DHA‐PC and DHA‐PS suppresses hepatic SREBP‐1c mediates lipogenesis and activates PPARα mediated fatty acid β‐oxidation in the liver. These data are the first to indicate that DHA‐PS has beneficial effects on age‐related lipid metabolism.

Practical Applications: The results obtained in this work might contribute to the understanding of biological activities of DHA enriched phospholipids and further investigation on its potential application values for food supplements.

This study investigates the effects of docosahexaenoic acid‐enriched phosphatidylcholine (DHA‐PC) and docosahexaenoic acid‐enriched phosphatidylserine (DHA‐PS) on age‐related lipid metabolic disorder in SAMP8 mice. The results shows that DHA‐PC and DHA‐PS improves age‐related lipometabolic disturbance by inhibiting hepatic fatty acid synthesis and enhancing hepatic fatty acid β‐oxidation, providing a reference for the development of functional ingredients rich in DHA phospholipids.
Why Tyrosol Derivatives Have to Be Quantified in the Calculation of “Olive Oil Polyphenols” Content to Support the Health Claim Provisioned in the EC Reg. 432/2012
Authors: Tsimidou Maria Z. , Nenadis Nikolaos , Servili Maurizio , García‐González Diego Luis , Gallina Toschi Tullia
Published: March 2018

The viewpoint is the outcome of the scientific expertise of the scientists that sign it and work collaboratively in the frame of the OLEUM project. The project aims to better guarantee olive oil quality and authenticity by empowering detection and fostering prevention of olive oil fraud and by an effort of harmonization, correct interpretation, and use of official and supporting analytical methods.

Practical Applications: The consensus among scientists, the European food authorities, IOC, and the olive industry on which compounds should be determined to support the health claim on olive oil polyphenols (EC Reg. 432/2012) is of utmost importance and can be supported by the evidence provided in this viewpoint article.

The exact interpretation of this health claim involves the clarification of the compounds that should be summed up to give the amount of at least 5 mg phenols per 20 g of oil.
Enhanced Donor–π–Acceptor Character of a Porphyrin Dye Incorporating Naphthobisthiadiazole for Efficient Near‐Infrared Light Absorption
Authors: Higashino Tomohiro , Kurumisawa Yuma , Nimura Shimpei , Iiyama Hitomi , Imahori Hiroshi
Published: March 2018

Donor–π–acceptor (D–π–A) molecules play an important role in various fields including polymer solar cells (PSCs) and dye‐sensitized solar cells (DSSCs). In PSCs, naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole (NTz) has emerged as a promising acceptor owing to its higher electron‐accepting ability compared with 2,1,3‐benzothiadiazole (BT), which is a widely used acceptor unit in DSSCs as well as PSCs. On the other hand, various D–π–A‐type porphyrin dyes have been developed for use in DSSCs and have achieved high power conversion efficiencies (η). Given that enhanced D–π–A character improves light‐harvesting ability in the near‐infrared (NIR) region, we have designed and synthesized for the first time a novel D–π–A‐type porphyrin sensitizer, ZnPNTz, incorporating the NTz unit. The porphyrin ZnPNTz shows excellent absorption in the NIR region together with a large Stokes shift as a result of the NTz moiety. A DSSC fabricated with ZnPNTz exhibits photocurrent generation at wavelengths up to 860 nm. Therefore, we have demonstrated that the NTz unit is a promising electron‐acceptor unit for novel D–π–A small molecules exhibiting unique optical properties in the NIR region.
Organocatalytic Strategies to Stereoselectively Trap Photochemically Generated Hydroxy‐o‐quinodimethanes
Authors: Cuadros Sara , Melchiorre Paolo
Published: March 2018

Light excitation of ortho‐alkyl aromatic ketones and aldehydes gives access to hydroxy‐o‐quinodimethanes. These reactive electron‐rich intermediates are sufficiently long‐lived to productively engage in chemical processes, mainly acting as dienes in [4+2]‐cycloadditions with electron‐poor alkenes. Since the early discovery of this photoenolization mechanism in 1961, a variety of transformations has been developed, providing a photochemical alternative to classical Diels–Alder chemistry. However, enantioselective catalytic versions of the photenolization/Diels–Alder sequence have remained elusive until recently. This review describes how the field of enantioselective organocatalysis has provided suitable tools to stereoselectively trap photochemically generated hydroxy‐o‐quinodimethanes. Recent studies have also demonstrated that the chemistry is not limited to cycloaddition‐type manifolds, but can be expanded in order to develop intermolecular enantioselective addition processes.
Frogolide – An Unprecedented Sesquiterpene Macrolactone from Scent Glands of African Frogs
Authors: Menke Markus , Melnik Kristina , Peram Pardha S. , Starnberger Iris , Hödl Walter , Vences Miguel , Schulz Stefan
Published: March 2018

Some amphibians use chemical signals in addition to optical and acoustical signals to transmit information. Males of mantellid frogs from Madagascar and hyperoliid frogs from Africa emit complex, species‐ and sex‐specific bouquets of volatiles from their femoral or gular glands. We report here on the identification, synthesis, and determination of the absolute configuration of a macrocyclic lactone occurring in several species of both families, (S)‐3,7,11‐dodec‐6,10‐dien‐12‐olide (S‐14, frogolide). Macrolides are a preferred compound class of frog volatiles. Nevertheless, frogolide is the first macrocyclic lactone obviously derived from the terpene pathway, in contrast to known frog macrolides that are usually formed via the fatty acid biosynthetic pathway.
N‐Aryl Imidazole Platforms – Synthesis and Structural Investigation
Authors: Adam Abdulselam , Mehrparvar Saber , Haberhauer Gebhard , Glüsenkamp Karl‐Heinz , Wölper Christoph
Published: March 2018

Cyclic oligomers of azole peptides were isolated from a multitude of marine organisms and were used for a variety of applications in supramolecular chemistry. Up to now the use of imidazole‐containing platforms based on Lissoclinum cyclopeptides were limited to N‐alkyl imidazole scaffolds. Here we present the synthesis of chiral N‐aryl imidazole amino acids by starting from the corresponding amidoketones and aniline derivatives. By using the optimized reaction conditions even chiral imidazoles with large substituents at the α‐carbon atom and at ortho position of the aryl ring were obtained without racemization at the stereogenic center. Subsequent one‐pot cyclotrimerization of the N‐aryl imidazole amino acids leads to the desired C3‐symmetric platforms in rather good yields. The investigation of the structures of the platforms with bromine atoms in ortho, meta and para position relative to the imidazole unit were conducted by NMR spectroscopy, X‐ray crystallography, and quantum chemical calculations. The experimental data reveals that the ortho isomer is present in a single conformer in which all bromine atoms are oriented in the same direction. The rotation around the aryl‐imidazole axis in this isomer is completely prevented in the measured temperature range.
Visible‐Light‐Mediated Eosin Y Photoredox‐Catalyzed Vicinal Thioamination of Alkynes: Radical Cascade Annulation Strategy for 2‐Substituted‐3‐sulfenylindoles
Authors: Tambe Shrikant D. , Rohokale Rajendra S. , Kshirsagar Umesh A.
Published: March 2018

An organic dye photoredox‐catalyzed regiospecific radical cascade annulation strategy of 2‐alkynyl‐azidoarenes to generate 3‐sulfenylindoles via vicinal thioamination of alkynes at room temperature, mediated by visible light, was developed. The method requires mild conditions, including visible light as a traceless green energy source, room temperature, eosin Y organic dye as a photoredox catalyst, ambient air as oxidant, and easily available starting materials to provide a green, efficient, metal‐ and strong‐oxidant‐free synthesis of 3‐sulfenylindoles with broad substrate scope through vicinal thioamination of alkynes.
Glycosylations of Simple Acceptors with 2‐O‐Acyl l‐Idose or l‐Iduronic Acid Donors Reveal Only a Minor Role for Neighbouring‐Group Participation
Authors: Mohamed Shifaza , He Qi Qi , Lepage Romain J. , Krenske Elizabeth H. , Ferro Vito
Published: March 2018

Several l‐idose and l‐iduronic acid glycosyl donors (mostly thioglycosides but also halides and trichloroacetimidates) with acyl protecting groups at the C‐2 position were prepared and evaluated in glycosylation reactions with simple acceptors. In glycosaminoglycan oligosaccharide syntheses in the literature, the presence of C‐2 acyl protecting groups in l‐ido‐configured glycosyl donors generally results in exclusive formation of 1,2‐trans glycosidic linkages, a finding that has typically been attributed to neighbouring‐group participation. However, glycosylations of simple alcohols with l‐ido‐configured donors (particularly thioglycosides), reported here, generally displayed incomplete stereocontrol and gave mixtures of the 1,2‐trans and 1,2‐cis products, suggesting that neighbouring‐group participation has lesser importance in these reactions. Glycosyl donors and reaction conditions were identified that gave improved, but not exclusive, selectivity for the desired α‐l‐anomer (1,2‐trans) as the major product. Interestingly, glycosylations under the same reaction conditions with more complex monosaccharide acceptors gave exclusively the expected 1,2‐trans products. The role of neighbouring‐group participation in these glycosylations was explored with density functional theory (DFT) calculations, which revealed that the non‐stereoselective addition of the acceptor alcohol to the intermediate oxocarbenium ion is competitive with the stereospecific addition of the acceptor to the acyloxonium ion intermediate.
Iron(III) Porphyrin Catalyzed Olefination of Aldehydes with 2,2,2‐Trifluorodiazoethane (CF3CHN2)
Authors: Lu Yang , Huang Chuyu , Liu Chao , Guo Yong , Chen Qing‐Yun
Published: March 2018

An efficient method for the iron(III) porphyrin catalyzed olefination of various aldehydes with 2,2,2‐trifluorodiazoethane under neutral conditions is described. This transformation was shown to have a broad substrate scope and provide the corresponding CF3‐substituted alkenes in good yields. The number of equivalents of PPh3 that is used in this reaction is crucial to the success of the olefination process. This reaction is a useful supplement to the synthetic applications of CF3CHN2.
2,4‐Bis(fluoroalkyl)quinoline‐3‐carboxylates as Tools for the Development of Potential Agrochemical Ingredients
Authors: Aribi Fallia , Panossian Armen , Vors Jean‐Pierre , Pazenok Sergii , Leroux Frédéric R.
Published: March 2018

Based on an easy and scalable method for the synthesis of quinoline derivatives substituted by fluorinated groups at both the C‐2 and C‐4 positions developed in our laboratory, we have devised an approach to the synthesis of a new series of unprecedented 2,4‐bis(fluoroalkyl)quinoline‐3‐carboxylates in just two steps. After standard saponification, the latter gave the corresponding 2,4‐bis(fluoroalkyl)quinoline‐3‐carboxylic acids, which served as pivotal intermediates for post‐functionalization reactions. Indeed, the carboxylic group could then be derivatized according to known procedures to introduce chemical diversity at the C‐3 position of these unprecedented structures. The resulting highly functionalized quinolines can serve as a platform for the development of biologically active molecules with strong potential for agrochemical research.
With a little help from our friends: The impact of cross‐group friendship on acculturation preferences
Authors: Hässler Tabea , González Roberto , Lay Siugmin , Lickel Brian , Zagefka Hanna , Tropp Linda R. , Brown Rupert , Manzi Astudillo Jorge , Bernardino Michelle
Published: March 2018

Despite extensive research on intergroup contact and acculturation, our understanding of how contact affects receiving society members’ preferences for acculturation orientation of immigrants over time is still relatively rudimentary. This longitudinal study examined how perceived group similarity and outgroup trust mediate the effects of cross‐group friendship on acculturation preferences (culture maintenance and culture adoption) of the receiving society. It was predicted that cross‐group friendship would affect acculturation preferences over time, and that these relationships would be partly mediated by outgroup trust and perceived group similarity. A three‐wave full longitudinal sample (N = 467 Chilean school students) was analyzed using structural equation modeling. Results confirmed that cross‐group friendship longitudinally predicted majority members’ support for the adoption of Chilean culture (via perceived group similarity) and Peruvian culture maintenance (via outgroup trust). Conceptual and practical implications are discussed.
A Green Approach to the Synthesis of Well‐structured Prussian Blue Cubes for the Effective Electrocatalytic Reduction of Antiprotozoal Agent Coccidiostat Nicarbazin
Authors: Akilarasan Muthumariappan , Kogularasu Sakthivel , Chen Shen‐Ming , Govindasamy Mani , Chen Tse‐Wei , Ali M. Ajmal , Al‐Hemaid Fahad M. A. , Elshikh M. S. , Farah M. Abul
Published: March 2018

For the first time, a robust electrochemical sensor to detect the coccidiostat nicarbazin (NCZ) is developed through the green synthesis of Prussian blue cubes from Volvariella volvacea (paddy straw mushroom) extract. Recently, numerous articles were reported about the issue that the prophylactic drugs were injected excessively as a feed additive for fattening the chickens in short period. It is a significant concern that the level of coccidiostat NCZ exceeds the residue limits in the tissues of the meat; mainly, in chicken and eggs. Therefore, it is crucial to develop a sensitive, reproducible and long‐lasting sensor for the real‐time detection of NCZ. Thus, we have generated an electrochemical sensor through the economic screen‐printed carbon electrode (SPCE) modification method. Eco‐friendly Prussian blue cubes are fabricated on the carbon film of SPCE. As a result, the modified electrode showed exceptional electrocatalytic ability towards NCZ and the reduction peak currents are correlated to the concentrations of NCZ. It retains the more extensive working range between 1.25×10−7 to 1.53×10−3 mol L−1, and it possesses a very low limit of detection as well as the appreciable sensitivity. This method is successfully applied to the recognition of NCZ in the samples of chicken meat and eggs.
Double Layer Impedance in Mixtures of Acetonitrile and Water
Authors: Aoki Koichi Jeremiah , Chen Jingyuan , Tang Peng
Published: March 2018

Double layer (DL) impedances were evaluated in mixed solutions of water and acetonitrile at various ratios in the polarized potential domain in order to find competitive orientation of the two solvent molecules on the platinum electrode. The DL capacitance at any ratio of the mixture shows the common power law of the ac‐frequency. The capacitance at molar fractions of water less than 0.2 increases linearly with the fraction, and reaches the value for aqueous solution. This variation indicates accumulation of water molecules on the electrode excluding acetonitrile molecules. It is modelled on the concept of the Langmuir‐type isotherm in which water and acetonitrile molecules have competitive interaction with the electrode. The experimental variations by the use of the isotherm yield the difference in the interaction energy, 6 kJ mol−1. The accumulation of water in the DL is supported by the formation of the adsorbed layer by insoluble ferrocene.
Determination of ellagic acid by capillary electrophoresis in Argentinian wines
Authors: Spisso Adrian , Gomez Federico J. V. , Fernanda Silva María
Published: March 2018

Rising interest in ellagic acid (EA) present in functional foods is supported by its antimutagenic, anticarcinogenic, antiviral, antibacterial and antioxidative effects. The present approach presents for the first time the determination of ellagic acid and other phenolics in wines by miniaturized solid phase extraction prior to capillary zone electrophoresis (CZE) with UV. The extraction was performed using a home‐made miniaturized pipette tip column. The procedure allowed a significant reduction in conditioning/sample/washing/elution volumes. The effects of important factors affecting the extraction efficiency as well as electrophoretic performance were investigated to acquire optimum conditions. The analytes were separated within 10 min with a BGE containing 30 mmol/L sodium tetraborate 10% v/v MeOH pH 9.10. The optimized method was applied to the determination of ellagic acid in commercial and pilot‐scale wines. Indeed, the content of EA was correlated with viticultural parameters such as grape varietal, production area, and aging conditions (oak wood guard and glass bottle ward). In order to validate the results, a comparison between the CZE and HPLC data was made.
Preparation and identification of oligosaccharides in lotus seeds and determination of their distribution in different parts of lotus
Authors: Chen Lingxiao , Hu Dejun , Liang Xiao , Zhao Jing , Li Shaoping
Published: March 2018

Three fractions (I–III) were separated from crude oligosaccharides of lotus seeds by fast protein liquid chromatography with final purity of 97.6, 96.3, and 96.8%, respectively. The fractions were identified as sucrose, raffinose, and stachyose by using TLC, HPLC with charged aerosol detector (CAD), LC‐MS, and methylation analysis. Subsequently sucrose and raffinose family oligosaccharides (RFOs) with degree of polymerization (DP) 3–5 (raffinose, stachyose, and verbascose) have been quantified by HPLC‐CAD for the first time. All calibration curves for investigated analytes showed good linear regression (R2 > 0.9952). Their limit of detection and limit of quantity were in the ranges 0.14−0.28 and 0.36−0.48 μg/mL, respectively. The recoveries ranged from 96.6 to 103.4%. The contents of sucrose and RFOs DP3–DP5 were different in lotus seeds and other parts of lotus samples, but similar in their own variety. Additionally, the distribution of RFOs in different parts of lotus were also compared and the results indicated that RFOs might be mainly synthesized in lotus seeds. This work is helpful for understanding the way of biosynthesis of RFOs in lotus as well as quality control of plants containing RFOs.