bluuebunny/crossref_metadata_2025 huggingface dataset:
Sequential crops for food, energy, and economic development in rural areas: the case of Sicily
Authors: Selvaggi Roberta , Valenti Francesca , Pappalardo Gioacchino , Rossi Lorella , Bozzetto Stefano , Pecorino Biagio , Dale Bruce E.
Published: November 2017

In this paper, we apply the principles of Biogasdoneright® to agriculture in Sicily (Italy), or more generally to Mediterranean agriculture. We propose new potential crop rotation schemes using Sorghum spp. drip irrigated second harvest and Italian sainfoin (Hedysarum coronarium L.) between two cycles of durum wheat to produce biogas and perhaps biomethane subsequently under the Biogasdoneright system. The Biogasdoneright system is a new model for sustainable biogas production based on sequential cropping and integration with food production. In Sicily, as in other Mediterranean countries, sequential crops and some perennial crops such as Opuntia spp. might be cultivated in environmentally critical areas prone to erosion, desertification, and fires. Therefore, biogas produced according to the crop rotation schemes as illustrated in this paper avoids competition with food and feed crops, while offering to the Sicilian agricultural sector many agronomic, economic, environmental, and social benefits. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
Experimental trials and ‘what works?’ in education: The case of grammar for writing
Authors: Wyse Dominic , Torgerson Carole
Published: November 2017

The place of evidence to inform educational effectiveness has received increasing attention internationally in the last two decades. An important contribution to evidence‐informed policy has been greater attention to experimental trials including randomised controlled trials (RCTs). The aim of this paper is to examine the use of evidence, particularly the use of evidence from experimental trials, to inform national curriculum policy. To do this the teaching of grammar to help pupils’ writing was selected as a case. Two well‐regarded and influential experimental trials that had a significant effect on policy, and that focused on the effectiveness of grammar teaching to support pupils’ writing, are examined in detail. In addition to the analysis of their methodology, the nature of the two trials is also considered in relation to other key studies in the field of grammar teaching for writing and a recently published robust RCT. The paper shows a significant and persistent mismatch between national curriculum policy in England and the robust evidence that is available with regard to the teaching of writing. It is concluded that there is a need for better evidence‐informed decisions by policy makers to ensure a national curriculum specification for writing that is more likely to have positive impact on pupils.
The PIWI‐Interacting RNA Molecular Pathway: Insights From Cultured Silkworm Germline Cells
Authors: Sakakibara Kazuhiro , Siomi Mikiko C.
Published: November 2017

The PIWI‐interacting RNA (piRNA) pathway, one of the major eukaryotic small RNA silencing pathways, is a genome surveillance system that silences selfish genes in animal gonads. piRNAs guide PIWI protein to target genes through Watson–Crick RNA–RNA base‐parings. Loss of piRNA function causes genome instability, inducing failure in gametogenesis and infertility. Studies using fruit flies and mice as key experimental models have resulted in tremendous progress in understanding the mechanism underlying the piRNA pathway. Recent work using cultured silkworm germline cells has also expanded our knowledge of piRNA biogenesis in particular, since these silkworm cells are the only cells of germline origin that can be cultured. In this review, we describe elucidation of the piRNA pathway using cultured silkworm cells as an experimental model by focusing on recent work in biochemistry and structural biology. Earlier studies that made important contributions to the field are also described.
Development and validation of a liquid chromatography–tandem mass spectrometry analytical method for the therapeutic drug monitoring of eight novel anticancer drugs
Authors: Herbrink M. , de Vries N. , Rosing H. , Huitema A. D. R. , Nuijen B. , Schellens J. H. M. , Beijnen J. H.
Published: November 2017

To support therapeutic drug monitoring of patients with cancer, a fast and accurate method for simultaneous quantification of the registered anticancer drugs afatinib, axitinib, ceritinib, crizotinib, dabrafenib, enzalutamide, regorafenib and trametinib in human plasma using liquid chromatography tandem mass spectrometry was developed and validated. Human plasma samples were collected from treated patients and stored at −20°C. Analytes and internal standards (stable isotopically labeled analytes) were extracted with acetonitrile. An equal amount of 10 mm NH4CO3 was added to the supernatant to yield the final extract. A 2 μL aliquot of this extract was injected onto a C18‐column, gradient elution was applied and triple‐quadrupole mass spectrometry in positive‐ion mode was used for detection. All results were within the acceptance criteria of the latest US Food and Drug Administration guidance and European Medicines Agency guidelines on method validation, except for the carry‐over of ceritinib and crizotinib. These were corrected for by the injection order of samples. Additional stability tests were carried out for axitinib and dabrafenib in relation to their reported photostability. In conclusion, the described method to simultaneously quantify the eight selected anticancer drugs in human plasma was successfully validated and applied for therapeutic drug monitoring in cancer patients treated with these drugs.
Comprehensive analysis of nine monoamines and metabolites in small amounts of peripheral murine (C57Bl/6 J) tissues
Authors: Nagler Joachim , Schriever Sonja C. , De Angelis Meri , Pfluger Paul T. , Schramm Karl‐Werner
Published: November 2017

Monoamines, acting as hormones and neurotransmitters, play a critical role in multiple physiological processes ranging from cognitive function and mood to sympathetic nervous system activity, fight‐or‐flight response and glucose homeostasis. In addition to brain and blood, monoamines are abundant in several tissues, and dysfunction in their synthesis or signaling is associated with various pathological conditions. It was our goal to develop a method to detect these compounds in peripheral murine tissues. In this study, we employed a high‐performance liquid chromatography method using electrochemical detection that allows not only detection of catecholamines but also a detailed analysis of nine monoamines and metabolites in murine tissues. Simple tissue extraction procedures were optimized for muscle (gastrocnemius, extensor digitorum longus and soleus), liver, pancreas and white adipose tissue in the range of weight 10–200 mg. The system allowed a limit of detection between 0.625 and 2.5 pg μL−1 for monoamine analytes and their metabolites, including dopamine, 3,4‐dihydroxyphenylacetic acid, 3‐methoxytyramine, homovanillic acid, norepinephrine, epinephrine, 3‐methoxy‐4‐hydroxyphenylglycol, serotonin and 5‐hydroxyindoleacetic acid. Typical concentrations for different monoamines and their metabolization products in these tissues are presented for C57Bl/6 J mice fed a high‐fat diet.
Engineered Biomolecular Recognition of RDX by Using a Thermostable Alcohol Dehydrogenase as a Protein Scaffold
Authors: Bulutoglu Beyza , Haghpanah Jennifer , Campbell Elliot , Banta Scott
Published: November 2017

There are many biotechnology applications that would benefit from simple, stable proteins with engineered biomolecular recognition. Here, we explored the hypothesis that a thermostable alcohol dehydrogenase (AdhD from Pyrococcus furiosus) could be engineered to bind a small molecule instead of a cofactor or molecules involved in the catalytic transition state. We chose the explosive molecule 1,3,5‐trinitro‐1,3,5‐triazine (royal demolition explosive, RDX) as a proof‐of‐concept. Its low solubility in water was exploited for immobilization for biopanning by using ribosome display. Docking simulations were used to identify two potential binding sites in AdhD, and a randomized library focused on tyrosine or serine mutations was used to determine that RDX was binding in the substrate binding pocket of the enzyme. A fully randomized binding pocket library was selected, and affinity maturation by error‐prone PCR led to the identification of a mutant (EP‐16) that gained the ability to bind RDX with an affinity of (73±11) μm. These results underscore the way in which thermostable enzymes can be useful scaffolds for expanding the biomolecular recognition toolbox.
Mechanistic Insights into Growth of Surface‐Mounted Metal‐Organic Framework Films Resolved by Infrared (Nano‐) Spectroscopy
Authors: Delen Guusje , Ristanović Zoran , Mandemaker Laurens D. B. , Weckhuysen Bert M.
Published: November 2017

Control over assembly, orientation, and defect‐free growth of metal‐organic framework (MOF) films is crucial for their future applications. A layer‐by‐layer approach is considered a suitable method to synthesize highly oriented films of numerous MOF topologies, but the initial stages of the film growth remain poorly understood. Here we use a combination of infrared (IR) reflection absorption spectroscopy and atomic force microscopy (AFM)‐IR imaging to investigate the assembly and growth of a surface mounted MOF (SURMOF) film, specifically HKUST‐1. IR spectra of the films were measured with monolayer sensitivity and <10 nm spatial resolution. In contrast to the common knowledge of LbL SURMOF synthesis, we find evidence for the surface‐hindered growth and large presence of copper acetate precursor species in the produced MOF thin‐films. The growth proceeds via a solution‐mediated mechanism where the presence of weakly adsorbed copper acetate species leads to the formation of crystalline agglomerates with a size that largely exceeds theoretical growth limits. We report the spectroscopic characterization of physisorbed copper acetate surface species and find evidence for the large presence of unexchanged and mixed copper‐paddle‐wheels. Based on these insights, we were able to optimize and automatize synthesis methods and produce (100) oriented HKUST‐1 thin‐films with significantly shorter synthesis times, and additionally use copper nitrate as an effective synthesis precursor.
Cobalt Pincer Complexes for Catalytic Reduction of Carboxylic Acid Esters
Authors: Junge Kathrin , Wendt Bianca , Cingolani Andrea , Spannenberg Anke , Wei Zhihong , Jiao Haijun , Beller Matthias
Published: November 2017

A selection of cobalt(I) and cobalt(II) pincer type complexes with different substitution patterns was tested in the catalytic reduction of carboxylic acid esters to alcohols. The cobalt pincer type complex 4 is suitable for the hydrogenation of aromatic as well as aliphatic and cyclic esters. Mechanistic investigation indicated a metal ligand cooperated reaction pathway.
Transcatheter or surgical aortic valve replacement in patients with advanced kidney disease: A propensity score–matched analysis
Authors: Doshi Rajkumar , Shah Jay , Patel Vaibhav , Jauhar Varun , Meraj Perwaiz
Published: November 2017

Background

Transcatheter aortic valve replacement (TAVR) is an alternative for surgically inoperable patients with severe aortic stenosis. Advanced kidney disease may significantly affect outcomes in patients treated with TAVR and surgical aortic valve replacement (SAVR).

Hypothesis

TAVR is associated with better in‐hospital outcomes compared with SAVR in patients with advanced kidney disease.

Methods

We identified our sample from the National Inpatient Sample between 2012 and 2014, using International Classification of Diseases, Ninth Revision, Clinical Modification codes. We included patients with chronic kidney disease stages IV and V and end‐stage renal disease as advanced kidney disease patients. We excluded patients with acute kidney injury on admission and patients on dialysis.

Results

After propensity matching, 2485 patients were included in each group. The primary outcome of in‐hospital mortality (12.9% vs 6.2%; P < 0.01) was higher with SAVR as compared with TAVR. Patients who underwent SAVR reported higher acute kidney injury (50.3% vs 33%; P < 0.01) and dialysis requirements (26.8% vs 20.1%; P < 0.01). Other secondary outcomes including blood transfusion, atrial fibrillation, iatrogenic cardiac complications, pericardial complications, perioperative stroke, perioperative infections, and postoperative shock were more common with SAVR. With SAVR, the length of hospitalization and hospitalization costs were significantly higher; however, permanent pacemaker placement was more common with TAVR compared with SAVR.

Conclusions

In patients with advanced kidney disease, SAVR was associated with higher mortality and higher periprocedural complications, as compared with TAVR. Thus, benefits of TAVR could be extended in patients with advanced kidney disease who cannot undergo surgery.
Leptomeningeal metastasis from systemic cancer: Review and update on management
Authors: Wang Nancy , Bertalan Mia S. , Brastianos Priscilla K.
Published: November 2017

Leptomeningeal metastasis is an uncommon and typically late complication of cancer with a poor prognosis and limited treatment options. Diagnosis is often challenging, with nonspecific presenting symptoms ranging from headache and confusion to focal neurologic deficits, such as cranial nerve palsies. Standard diagnostic evaluation involves a neurologic examination, magnetic resonance imaging of the brain and spine with gadolinium, and cytologic evaluation of the cerebral spinal fluid. Therapy entails a multimodal approach focused on palliation with surgery, radiation, and/or chemotherapy, which may be administered systemically or directly into the cerebral spinal fluid. Limited trial data exist to guide treatment, and current regimens are based primarily on expert opinion. Although newer targeted and immunotherapeutic agents are under investigation and have shown promise, an improved understanding of the biology of leptomeningeal metastasis and treatment resistance as well as additional randomized controlled studies are needed to guide the optimal treatment of this devastating disease. Cancer 2018;124:21‐35. © 2017 American Cancer Society.
Factors affecting compliance with confirmatory colonoscopy after a positive fecal immunochemical test in a national colorectal screening program
Authors: Cheng Shao‐Yi , Li Ming‐Chieh , Chia Shu‐Li , Huang Kuo‐Chin , Chiu Tai‐Yuan , Chan Ding‐Cheng , Chiu Han‐Mo
Published: November 2017

BACKGROUND

Screening with the fecal immunochemical test (FIT) is effective in reducing deaths from colorectal cancer (CRC). Since 2004, biennial FIT screening has been available to a target population in Taiwan as a national screening program. The objective of the current study was to identify the factors that influence willingness to undergo a confirmatory colonoscopy after a positive FIT, because related references in the published literature were scarce.

METHODS

A semistructured questionnaire was based on the Health Belief Model (HBM) and a literature review. A stratified, random sampling method was used to recruit participants who had a positive FIT from all cities/counties in Taiwan. Cross‐sectional, computer‐assisted telephone interviews were conducted in 2012, and the results were analyzed using a logistic regression model that took into account population demographics, core content of the HBM, and HBM‐modifying variables.

RESULTS

In total, 2807 respondents were included in the analysis. The completion rate was 50%. Multivariate analyses revealed that higher perceived threat (adjusted odds ratio [aOR], 1.62; 95% confidence interval [CI], 1.31‐2.01), higher cues for action (aOR, 2.18; 95% CI, 1.68‐1.82), lower perceived barriers (aOR, 0.42; 95% CI, 0.34‐0.42) and higher health behavior scores (aOR, 1.30; 95% CI, 1.05‐1.60) were associated with a greater willingness to participate in confirmatory colonoscopy. Participants who were older (aOR, 0.74; 95% CI, 0.55‐0.98) or unmarried (aOR, 0.72; 95% CI, 0.56‐0.92) were less likely to participate in verification.

CONCLUSIONS

The government could improve the screening rate by training case managers to assist in following patients until they complete colonoscopy, subsidizing sedated colonoscopies, and providing health education not only to the general public but also to physicians.Cancer2018;124:907‐15. ©2017 American Cancer Society.
Fuzzy ACID properties for self‐adaptive composite cloud services execution
Authors: Cardinale Yudith , El Haddad Joyce , Manouvrier Maude , Rukoz Marta
Published: November 2017

The ACID transaction model has played a cornerstone role in service composition to guarantee that composite services (CSs) have transactional support and consistent outcomes even in presence of failures. However, the classical ACID properties are too restrictive for independent and multi‐proprietors services running on distributed environments, such clouds. Transactional properties allow a relaxed atomicity and isolation, providing an “all‐or‐(almost)nothing” model. In previous works, we proposed a model to relax atomicity, called fuzzy atomicity, according user requirements (acceptable fuzzy atomicity). In this article, we extend that model and propose an approach to measure the fuzzy atomicity. Our model allows to self‐adapt the CS execution, taking into account the state of the CS execution and user preferences (ie, the acceptable fuzzy atomicity expressed in the user requirements). This fuzzy atomicity measure is applied in a self‐adaptive CS execution model based on the transactional properties (pivot, compensatable, and retriable) of its component services and on a checkpointing mechanism. It is suitable to cloud computing, which offers cloud services on demand and in which CS execution should preserve the self‐organizing and self‐adaptivity properties of such environment, specially in the presence of failures. We show how it is possible to relax the retriable property in CSs execution, based on our fuzzy atomicity model. Additionally, in this work, we present a comparative analysis of the most recent works in the context of ACID properties relaxation for CS.
Constructing virtual 5‐dimensional tori out of lower‐dimensional network cards
Authors: Andújar Francisco J. , Villar Juan A. , Sánchez José L. , Alfaro Francisco J. , Duato José , Fröning Holger
Published: November 2017

In the Top500 and Graph500 lists of the last years, some of the most powerful systems implement a torus topology to interconnect the millions of computing nodes they include. Some of these torus networks are of five or six dimensions, which implies an additional difficulty as the node degree increases. In previous works, we proposed and evaluated the nD Twin (nDT) torus topology to virtually increase the dimensions a torus is able to implement. We showed that this new topology reduces the distances between nodes, increasing, therefore, global network performance. In this work, we present how to build a 5DT torus network using a specific commercial 6‐port network card (EXTOLL card) to interconnect those nodes. We show, using the same number of cards, that the performance of the 5DT torus network we are able to implement using our proposal is higher than the performance of the 3D torus network for the same number of compute nodes.
Spectroscopic Engineering toward Near‐Infrared Absorption of Materials Containing Perylene Diimide
Authors: Cann Jonathan R. , Cabanetos Clement , Welch Gregory C.
Published: November 2017

The ability to tune the dye structure synthetically has been crucial in the development of materials with tailored properties for given applications. In this contribution, a series of discrete molecules are reported, which are constructed from the perylene diimide (PDI) chromophore and three dyes, namely thienyl diketopyrrolopyrrole (DPPTh2), pyridyl diketopyrrolopyrrole (DPPPyr2), and thienoisoindigo (TII). Through the choice of dye molecule and linking of the dye and PDI through conjugated acetylene bridges, the light‐harvesting characteristics can be engineered to exhibit optical absorption in the range 300–900 nm. Each molecule shows ambipolar redox behavior, leading to unique electrochromic behavior.
Generic Versions of Narrow Therapeutic Index Drugs: A National Survey of Pharmacists' Substitution Beliefs and Practices
Authors: Sarpatwari Ameet , Lee Moa P. , Gagne Joshua J. , Lu Zhigang , Dutcher Sarah K. , Jiang Wenlei , Campbell Eric G. , Kesselheim Aaron S.
Published: November 2017

Small changes in bioavailability of narrow therapeutic index (NTI) drugs can alter clinical outcomes, raising concern over generic NTI substitution. We surveyed pharmacists to identify their perceptions of generic NTI drugs, their frequency of performing generic NTI substitution, and predictors of this behavior. Of 710 respondents (33% response rate), 87% perceived generic NTI drugs as effective as their brand‐name versions and 94% as safe. Whereas 82% almost always performed generic NTI substitution for initial prescriptions, only 60% did for refills. Pharmacists in non‐chain settings (odds ratio (OR) = 2.37; 95% confidence interval (CI) = 1.40–4.02), in practice longer (per year OR = 1.04; 95% CI = 1.02–1.06), in states with affirmative patient consent laws (OR = 1.88; 95% CI = 1.06–3.32), and in states with NTI‐specific substitution requirements (OR = 1.95; 95% CI = 1.16–3.26) were more likely not to substitute initial prescriptions. Education of non‐chain and veteran pharmacists and elimination of affirmative patient consent and NTI‐specific substitution requirements could increase generic NTI substitution.
Evaluation of markers out of the steroid profile for the screening of testosterone misuse. Part II: Intramuscular administration
Authors: Kotronoulas Aristotelis , Gomez‐Gómez Àlex , Fabregat Andreu , Segura Jordi , Yang Sheng , Xing Yanyi , Moutian Wu , Marcos Josep , Joglar Jesús , Ventura Rosa , Pozo Oscar J.
Published: November 2017

In the fight against doping, the introduction of alternative markers to the steroid profile can be considered as an effective approach to improve the screening capabilities for the detection of testosterone (T) misuse. The aim of this study was to evaluate the potential of several T metabolites (cysteinyl conjugated and glucuronoconjugated resistant to enzymatic hydrolysis) to detect both the transdermal and the intramuscular administration of T. In Part I of the study, we studied the potential of these metabolites for the detection of T transdermal administration. Results revealed that resistant glucuronides can be a suitable complement to the current steroid profile. In this, Part II, dedicated to the intramuscular administration, we studied the potential of cysteinyl conjugated, resistant glucuronoconjugated and 1‐cyclopentenoylglycine (1‐CPG) for the detection of a single intramuscular injection of T cypionate. Possible differences in the excretion profile of all markers were explored between individuals with low basal (n=6) and medium basal (n=6) values of the testosterone/epitestosterone ratio (T/E). The results showed that all tested markers presented low intra‐individual stability in basal conditions. Despite this, all glucuronoconjugated markers and 1‐CPG, but not the cysteinyl conjugated markers, provided detection windows that were similar or longer than those obtained by markers currently included in the steroid profile. Based on the results obtained from the 2 parts of this study and from previously reported data, the potential applicability and the limitations of including these markers in the steroid profile are discussed.
Wild bee and floral diversity co‐vary in response to the direct and indirect impacts of land use
Authors: Papanikolaou Alexandra D. , Kühn Ingolf , Frenzel Mark , Kuhlmann Michael , Poschlod Peter , Potts Simon G. , Roberts Stuart P. M. , Schweiger Oliver
Published: November 2017

Loss of habitat area and diversity poses a threat to communities of wild pollinators and flowering plants in agricultural landscapes. Pollinators, such as wild bees, and insect‐pollinated plants are two groups of organisms that closely interact. Nevertheless, it is still not clear how species richness and functional diversity, in terms of pollination‐relevant traits, of these two groups influence each other and how they respond to land use change. In the present study, we used data from 24 agricultural landscapes in seven European countries to investigate the effect of landscape composition and habitat richness on species richness and functional diversity of wild bees and insect‐pollinated plants. We characterized the relationships between the diversity of bees and flowering plants and identified indirect effects of landscape on bees and plants mediated by these relationships. We found that increasing cover of arable land negatively affected flowering plant species richness, while increasing habitat richness positively affected the species richness and functional diversity of bees. In contrast, the functional diversity of insect‐pollinated plants (when corrected for species richness) was unaffected by landscape composition, and habitat richness showed little relation to bee functional diversity. We additionally found that bee species richness positively affected plant species richness and that bee functional diversity was positively affected by both species richness and functional diversity of plants. The relationships between flowering plant and bee diversity were modulated by indirect effects of landscape characteristics on the biotic communities. In conclusion, our findings demonstrate that landscape properties affect plant and bee communities in both direct and indirect ways. The interconnection between the diversities of wild bees and insect‐pollinated plants increases the risk for parallel declines, extinctions, and functional depletion. Our study highlights the necessity of considering the interplay between interacting species groups when assessing the response of entire communities to land use changes.
The 2‐(4‐Phenyl‐1H‐1,2,3‐triazol‐1‐yl)ethanol‐Based Phosphinite Ligand Ph2POCH2CH2[1,2,3‐N3C(Ph)C(H)] – Synthesis, Transition‐Metal Complexes, and Structural Studies
Authors: Choubey Bimba , Prasad Pandey Sameer , Mague Joel T. , Balakrishna Maravanji S.
Published: November 2017

The synthesis and coordination complexes of the new 1,2,3‐triazole phosphinite Ph2POCH2CH2[1,2,3‐N3C(Ph)C(H)] (2) are described. Compound 2 reacts with H2O2, S8, and Se8 to afford the chalcogenides Ph2P(=E)OCH2CH2[1,2,3‐N3C(Ph)C(H)] [E = O (3), S (4), and Se (5)]. The reaction of 2 with [Ru(η6‐cymene)Cl2] yielded [Ru(η6‐cymene)Cl2(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})] (6), which produced [Ru(η6‐cymene)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})]2[OTf]2 (7) on further treatment with silver triflate (AgOTf); in 7, 2 acts as a bidentate (P,N) ligand. The reaction of 2 with [CpRuCl(PPh3)2] (Cp = cyclopentadienyl) in 1:1 and 1:2 molar ratios afforded the mono‐ and disubstituted complexes [CpRuCl(PPh3)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})] (8) and [CpRuCl(Ph2P‐OCH2CH2{1,2,3‐N3C(Ph)C(H)})2] (9), respectively. Complex 9 reacted with silver triflate to yield the cationic complex [CpRu(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})][OTf] (10), in which one of the phosphinite ligands shows P,N‐chelation. The reactions of 2 with [M(COD)Cl2] (M = Pd, Pt; COD = 1,5‐cyclooctadiene) in 2:1 ratios yielded cis‐[MCl2(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})2] [M = Pd (11) and Pt (12)]. The similar reaction of 2 with [PdCl(η3‐C3H5)]2 in a 2:1 ratio afforded [PdCl(η3‐C3H5)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})] (13). The reaction of 2 with [AuCl(SMe2)] in a 1:1 ratio yielded [Au(Cl)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})2] (14). The molecular structures of 6, 7, 9, 11, and 12 were determined by single‐crystal X‐ray studies.
A Two‐Dimensional Metal–Organic Framework as a Fluorescent Probe for Ascorbic Acid Sensing
Authors: Yue Dan , Huang Yike , Zhang Jun , Zhang Xin , Cui Yuanjing , Yang Yu , Qian Guodong
Published: November 2017

Ascorbic acid (AA) is an important biological molecule, but the detection of AA is still a huge challenge. Therefore, highly sensitive and selective fluorescent sensors for AA determination are urgently demanded. In this work, the new organic linker 4,4′‐(1H‐pyrazole‐1,3‐diyl)dibenzoic acid (H2L) was prepared to construct the new two‐dimensional metal–organic framework (MOF) ZnL(H2O) (ZJU‐137, ZJU = Zhejiang University). The ZJU‐137 MOF demonstrates high selectivity and sensitivity for the detection of AA through fluorescence quenching. The detection limit for AA was 34 nM, and a wide linear concentration‐dependent response (0–60 µm) was observed; hence, ZJU‐137 has promising potential for the determination of AA in practical applications.
The Diverse Reactivity of Homopropargylic Amines as “Masked” 1C Synthons for the Aza‐Friedel–Crafts Alkylation of Indoles
Authors: Chen Hao , Ni Min , Bao Xiaofeng , Wang Chan , Liu Lingyan , Chang Weixing , Li Jing
Published: November 2017

A novel type of “masked” 1C synthon was developed through the hydroamination cyclization‐protonation of homopropargylic amines to act as aza‐Friedel–Crafts alkylation reagents to react with indoles. A variety of 3‐(2‐pyrrolidinyl)indoles were generated in good to high yields. More significantly, some of the corresponding products display potential bioactivity against chlamydial infection, wherein they specifically target the mid‐stage of the chlamydial life cycle by interfering with RB replication.
‘Local gradient’ and between‐site variability of erosion rate on badlands in the Karoo, South Africa
Authors: Favis‐Mortlock David , Boardman John , Foster Ian , Greenwood Philip
Published: November 2017

Site‐average values of local gradient, defined as the steepest slope angle measured at a point, are a powerful predictor of long‐term rates of soil loss as measured by erosion pins on the non‐channel floor portions of ten badland study sites in the Karoo area of South Africa. Local gradient may be easily measured using a smartphone clinometer. The successful use of local gradient here is in strong contrast to the previous failure of other site‐specific attributes, including other measures of gradient and relief, to explain between‐site variation in erosion rate on these study sites.

Each measurement of local gradient may be thought of as a sample of the site's microtopography. Microrelief is a strong determinant of the emergent patterns of inter‐channel overland flow, and hence of the patterns of inter‐channel erosion by flow. Local gradient changes most rapidly during the initial stages of channel incision. When channels are established, local gradient changes more slowly leading to almost‐parallel retreat of channel sidewalls.

A sensitivity analysis suggests that measurements of local gradient are not all equal with regard to prediction of long‐term erosion rate. A greater share of predictive power is contributed by measurements made on very steep or vertical channel side wall areas, and a lesser share is contributed by measurements made on interfluves. Copyright © 2017 John Wiley & Sons, Ltd.
Reproducibility ofEEG‐MEGfusion source analysis of interictal spikes: Relevance in presurgical evaluation of epilepsy
Authors: Chowdhury Rasheda Arman , Pellegrino Giovanni , Aydin Ümit , Lina Jean‐Marc , Dubeau François , Kobayashi Eliane , Grova Christophe
Published: November 2017

Fusion of electroencephalography (EEG) and magnetoencephalography (MEG) data using maximum entropy on the mean method (MEM‐fusion) takes advantage of the complementarities between EEG and MEG to improve localization accuracy. Simulation studies demonstrated MEM‐fusion to be robust especially in noisy conditions such as single spike source localizations (SSSL). Our objective was to assess the reliability of SSSL using MEM‐fusion on clinical data. We proposed to cluster SSSL results to find the most reliable and consistent source map from the reconstructed sources, the so‐calledconsensus map. Thirty‐four types of interictal epileptic discharges (IEDs) were analyzed from 26 patients with well‐defined epileptogenic focus. SSSLs were performed on EEG, MEG, and fusion data and consensus maps were estimated using hierarchical clustering. Qualitative (spike‐to‐spike reproducibility rate, SSR) and quantitative (localization error and spatial dispersion) assessments were performed using the epileptogenic focus as clinical reference. Fusion SSSL provided significantly better results than EEG or MEG alone. Fusion found at least one cluster concordant with the clinical reference in all cases. This concordant cluster was always the one involving the highest number of spikes. Fusion yielded highest reproducibility (SSR EEG = 55%, MEG = 71%, fusion = 90%) and lowest localization error. Also, using only few channels from either modality (21EEG + 272MEG or 54EEG + 25MEG) was sufficient to reach accurate fusion. MEM‐fusion with consensus map approach provides an objective way of finding the most reliable and concordant generators of IEDs. We, therefore, suggest the pertinence of SSSL using MEM‐fusion as a valuable clinical tool for presurgical evaluation of epilepsy.
Estimating restorable wetland water storage at landscape scales
Authors: Jones Charles Nathan , Evenson Grey R. , McLaughlin Daniel L. , Vanderhoof Melanie K. , Lang Megan W. , McCarty Greg W. , Golden Heather E. , Lane Charles R. , Alexander Laurie C.
Published: November 2017

Globally, hydrologic modifications such as ditching and subsurface drainage have significantly reduced wetland water storage capacity (i.e., volume of surface water a wetland can retain) and consequent wetland functions. While wetland area has been well documented across many landscapes and used to guide restoration efforts, few studies have directly quantified the associated wetland storage capacity. Here, we present a novel raster‐based approach to quantify both contemporary and potential (i.e., restorable) storage capacities of individual depressional basins across landscapes. We demonstrate the utility of this method by applying it to the Delmarva Peninsula, a region punctuated by both depressional wetlands and drainage ditches. Across the entire peninsula, we estimated that restoration (i.e., plugging ditches) could increase storage capacity by 80%. Focusing on an individual watershed, we found that over 59% of restorable storage capacity occurs within 20 m of the drainage network, and that 93% occurs within 1 m elevation of the drainage network. Our demonstration highlights widespread ditching in this landscape, spatial patterns of both contemporary and potential storage capacities, and clear opportunities for hydrologic restoration. In Delmarva and more broadly, our novel approach can inform targeted landscape‐scale conservation and restoration efforts to optimize hydrologically mediated wetland functions.
Delineation of flood generating processes and their hydrological response
Authors: Keller Luise , Rössler Ole , Martius Olivia , Weingartner Rolf
Published: November 2017

Knowledge about flood generating processes can be beneficial for numerous applications. Especially in the context of climate change impact assessment, daily patterns of meteorological and catchment state conditions leading to flood events (i.e., storylines) may be of value. Here, we propose an approach to identify storylines of flood generation using daily weather and snow cover observations. The approach is tested for and applied to a typical pre‐Alpine catchment in the period between 1961 and 2014. Five precipitation parameters were determined that describe temporal and spatial characteristics of the flood associated precipitation events. The catchment's snow coverage was derived using statistical relationships between a satellite‐derived snow cover climatology and station snow measurements. Moreover, (pre‐) event snow melt sums were estimated using a temperature‐index model. Based on the precipitation and catchment state parameters, 5 storylines were identified with a cluster analysis: These are (a) long duration, low intensity precipitation events with high precipitation depths, (b) long duration precipitation events with high precipitation depths and episodes of high intensities, (c) shorter duration events with high or (d) low precipitation intensity, respectively, and (e) rain‐on‐snow events. The event groups have distinct hydrological characteristics that can largely be explained by the storylines' respective properties. The long duration, high intensity storyline leads to the most adverse hydrological response, namely, a combination of high peak magnitudes, high volumes, and long durations of threshold exceedance. The results show that flood generating processes in mesoscale catchments can be distinguished on the basis of daily meteorological and catchment state parameters and that these process types can explain the hydrological flood properties in a qualitative way. Hydrological simulations of daily resolution can thus be analysed with respect to flood generating processes.
Impacts of climate change on the discharge and glacier mass balance of the different glacierized watersheds in the Tianshan Mountains, Central Asia
Authors: Xu Min , Wu Hao , Kang Shichang
Published: November 2017

The Tianshan Mountains represent an important water source for the arid and semi‐arid regions of Central Asia. The discharge and glacier mass balance (GMB) in the Tianshan Mountains are sensitive to changes in climate. In this study, the changes in temperature, precipitation, and discharge of six glacierized watersheds of Tianshan Mountains were explored using non‐parametric tests and wavelet transforms during 1957–2004. On the basis of the statistical mechanics and maximum entropy principle model, the GMB at the watershed scale were reconstructed for the study period. The discharge and GMB responses to climate change were examined in different watersheds. The results showed that regional climate warming was obvious, especially after 1996. The warming trend increased gradually from east to west, and the increase in temperature was greater on the north slope than on the south slope. The changing trends in precipitation increased from eastern region to central region, and then, the trend decreased in the western region, although the value was higher than that in the eastern region. The discharge presented significant periods of 2.7–5.4 years and increased from east to west. Significant periodicity indicated that the discharge in the different watersheds exhibited obviously different patterns. The GMB losses were larger in south and east than in north. The large glaciers had more stable interannual variations in discharge, and large fluctuations in discharge will be observed as the glacier areas shrink. Precipitation was the dominant factor for discharge during the study period, although the influence of increasing temperatures on hydrological regimes should not be neglected in the long term. Systematic differences in discharge and the GMB in glacierized watersheds in response to climate change are apparent in the Tianshan Mountains.
Immunoglobulin G; structure and functional implications of different subclass modifications in initiation and resolution of allergy
Authors: Scott‐Taylor Timothy H. , Axinia Stefan‐Claudiu , Amin Sumeya , Pettengell Ruth
Published: November 2017

IgE and not IgG is usually associated with allergy. IgE lodged on mast cells in skin or gut and basophils in the blood allows for the prolonged duration of allergy through the persistent expression of high affinity IgE receptors. However, many allergic reactions are not dependent on IgE and are generated in the absence of allergen specific and even total IgE. Instead, IgG plasma cells are involved in induction of, and for much of the pathogenesis of, allergic diseases. The pattern of IgG producing plasma cells in atopic children and the tendency for direct or further class switching to IgE are the principle factors responsible for long‐lasting sensitization of mast cells in allergic children. Indirect class switching from IgG producing plasma cells has been shown to be the predominant pathway for production of IgE while a Th2 microenvironment, genetic predisposition, and the concentration and nature of allergens together act on IgG plasma cells in the atopic tendency to undergo further immunoglobulin gene recombination. The seminal involvement of IgG in allergy is further indicated by the principal role of IgG4 in the natural resolution of allergy and as the favourable immunological response to immunotherapy. This paper will look at allergy through the role of different antibodies than IgE and give current knowledge of the nature and role of IgG antibodies in the start, maintenance and resolution of allergy.
Noninvasive, high‐speed, near‐infrared imaging of the biomolecular distribution and molecular mechanism of embryonic development in fertilized fish eggs
Authors: Ishigaki Mika , Nishii Takashi , Puangchit Paralee , Yasui Yui , Huck Christian W. , Ozaki Yukihiro
Published: November 2017

In this study, the distribution of biomaterials and its molecular mechanism of embryonic development in Japanese medaka fish were analyzed nondestructively and noninvasively without staining using near‐infrared (NIR) imaging. The microscopic NIR imaging system used in this research was a device capable of ultra‐high‐speed imaging; using this system, one can acquire microscopic imaging data in a few seconds. Therefore, the medaka eggs remained alive throughout measurements and were successfully monitored in vivo. The distributions of biomolecules were examined by mapping the intensities of NIR bands resulting from lipids, proteins and water in 2 dimensions (2D). The structures of eyes, lipid bilayer membranes, micelles and water‐structure differences at the interface of different substances constituting different structures on the egg were visualized. Furthermore, insights on the metabolic mechanisms of lipids and membrane functions were drawn from the biased distribution of lipoproteins and the presence of unsaturated fatty acids in the egg membrane. These results indicated the potential for NIR imaging in evaluating the biological functions and metabolic systems of cells and embryos.
Possible protective mechanisms exerted by metformin or metformin and vitamin E in isoproterenol‐induced cardiac injury
Authors: Al‐Rasheed Nawal M. , Al‐Rasheed Nouf M. , AL‐Rabeeah Danah A. , AL‐Barrak Heba S. , AL‐Salman Salma A. , Ibrahim Shahd A. , AL‐Hassab Sulafa A. , Al‐Amin Maha A. , Hasan Iman H. , Al‐Ajmi Hanaa N. , AL‐Shammari Tahani K.
Published: November 2017

Several studies have reported that metformin is cardioprotective for diabetic and non‐diabetic ischemic hearts through mechanisms that cannot be entirely attributed to its anti‐hyperglycemic effect. This study was designed to investigate the cardioprotective effects of metformin with and without vitamin E after induction myocardial infarction (MI) in rats, using isoproterenol. Administration of metformin or vitamin E significantly reduced the cardiac mass index (P < 0.01), ameliorated the changes to cardiac biomarkers, and attenuated oxidative stress levels compared to the isoproterenol group. Interestingly, combination therapy showed a slight synergistic effect. Histopathological analysis suggested that metformin treatment reduced NF‐κB expression and protected against isoproterenol‐induced MI. Our results indicate that metformin mediates a cardioprotective effect against isoproterenol‐induced MI via antioxidant activity and modulation of the NF‐κB signaling pathway. This suggests that metformin would be beneficial in MI treatment.
Testing the limits of model membrane simulations—bilayer composition and pressure scaling
Authors: Ivanova Nikoleta , Ivanova Anela
Published: November 2017

Studying transfer of bioactive compounds across cell membranes by simulations attracts growing attention. To perform such calculations accurately, it is necessary to verify the validity of computational protocols established for description of unperturbed lipid bilayers also with translocating substances present. The current work reports the results from 1 μs long atomistic molecular dynamics simulations of two types of model plasma membranes—one built of a single phospholipid (DPPC) and one constructed of four types of phospholipids—in the presence of a drug‐peptide complex experimentally known to cross cell membranes. The influence of membrane composition and of applied pressure scaling algorithm on the simulations outcome is analyzed with particular focus on membrane structure and on complex‐lipid interactions during the initial penetration stage. It is found that the mixed composition of the membrane is important for correct assessment of the interactions with the complex both from purely structural perspective and because of the uneven charge distribution. The structure of the mixed lipid bilayer is affected more markedly by the pressure scaling algorithm. When the pressure is isotropically scaled, lipids are distributed almost homogeneously along the membrane in liquid ordered state. On semi‐isotropic scaling, the lipid tails undergo significant rearrangement and a long‐range ordered state is established. This results in “freezing” of the membrane and expulsion of the complex. The statistical analysis of the MD data points to the conclusion that a mixed‐lipid membrane model with isotropic pressure scaling would be more suitable for describing the process of complex translocation across neoplastic membranes. © 2017 Wiley Periodicals, Inc.
Analytic energy gradients for orbital‐optimized MP3 and MP2.5 with the density‐fitting approximation: An efficient implementation
Authors: Bozkaya Uğur
Published: November 2017

Efficient implementations of analytic gradients for the orbital‐optimized MP3 and MP2.5 and their standard versions with the density‐fitting approximation, which are denoted as DF‐MP3, DF‐MP2.5, DF‐OMP3, and DF‐OMP2.5, are presented. The DF‐MP3, DF‐MP2.5, DF‐OMP3, and DF‐OMP2.5 methods are applied to a set of alkanes and noncovalent interaction complexes to compare the computational cost with the conventional MP3, MP2.5, OMP3, and OMP2.5. Our results demonstrate that density‐fitted perturbation theory (DF‐MP) methods considered substantially reduce the computational cost compared to conventional MP methods. The efficiency of our DF‐MP methods arise from the reduced input/output (I/O) time and the acceleration of gradient related terms, such as computations of particle density and generalized Fock matrices (PDMs and GFM), solution of the Z‐vector equation, back‐transformations of PDMs and GFM, and evaluation of analytic gradients in the atomic orbital basis. Further, application results show that errors introduced by the DF approach are negligible. Mean absolute errors for bond lengths of a molecular set, with the cc‐pCVQZ basis set, is 0.0001–0.0002 Å. © 2017 Wiley Periodicals, Inc.