bluuebunny/crossref_metadata_2025 huggingface dataset:
A Stable Seven‐Membered Heterocycle, Containing B, C, N, O, and P Atoms, inside a Smaragdyrin Macrocycle
Authors: Kalita Hemanta , Lee Way‐Zen , Theophall Gregory G. , Lakshmi K. V. , Ravikanth M.
Published: July 2015

Unprecedented examples of smaragdyrin macrocycles containing seven membered heterocyclic rings were synthesized under simple reaction conditions in high yields. The heterocycle formed inside smaragdyrin macrocycle is rare example of heterocycle containing five different atoms, such as B, C, N, O, and P atoms. The mixed BIII and PV complexes of smaragdyrin macrocycles showed new structural, spectral, and electrochemical properties.
Dynamic Covalent Organocatalysts Discovered from Catalytic Systems through Rapid Deconvolution Screening
Authors: Schaufelberger Fredrik , Ramström Olof
Published: July 2015

The first example of a bifunctional organocatalyst assembled through dynamic covalent chemistry (DCC) is described. The catalyst is based on reversible imine chemistry and can catalyze the Morita–Baylis–Hillman (MBH) reaction of enones with aldehydes or N‐tosyl imines. Furthermore, these dynamic catalysts were shown to be optimizable through a systemic screening approach, in which large mixtures of catalyst structures were generated, and the optimal catalyst could be directly identified by using dynamic deconvolution. This strategy allowed one‐pot synthesis and in situ evaluation of several potential catalysts without the need to separate, characterize, and purify each individual structure. The systems were furthermore shown to catalyze and re‐equilibrate their own formation through a previously unknown thiourea‐catalyzed transimination process.
Drug Delivery Nanocarriers from a Fully Degradable PEG‐Conjugated Polyester with a Reduction‐Responsive Backbone
Authors: Yameen Basit , Vilos Cristian , Choi Won Il , Whyte Andrew , Huang Jining , Pollit Lori , Farokhzad Omid C.
Published: July 2015

The remarkably high intracellular concentration of reducing agents is an excellent endogenous stimulus for designing nanocarriers programmed for intracellular delivery of therapeutic agents. However, despite their excellent biodegradability profiles, aliphatic polyesters that are fully degradable in response to the intracellular reducing environment are rare. Herein, a reduction‐responsive drug delivery nanocarrier derived from a linear polyester bearing disulfide bonds is reported. The reduction‐responsive polyester is synthesized via a convenient polycondensation process. After conjugation of terminal carboxylic acid groups of polyester to polyethylene glycol (PEG), the resulting polymer self‐assembles into nanoparticles that are capable of encapsulating dye and anticancer drug molecules. The reduction‐responsive nanoparticles display a fast payload release rate in response to the intracellular reducing environment, which translates into superior anticancer activity towards PC‐3 cells.
Total Synthesis of cis‐Clavicipitic Acid from Asparagine via Ir‐Catalyzed CH bond Activation as a Key Step
Authors: Tahara Yu‐ki , Ito Mamoru , Kanyiva Kyalo Stephen , Shibata Takanori
Published: July 2015

4‐Substituted tryptophan derivatives and the total synthesis of cis‐clavicipitic acid were achieved in reactions in which Ir‐catalyzed CH bond activation was a key step. The starting material for these reactions is asparagine, which is a cheap natural amino acid. The reductive amination step from the 4‐substituted tryptophan derivative gave cis‐clavicipitic acid with perfect diastereoselectivity.
A Versatile Approach to CF3‐Containing 2‐Pyrrolidones by Tandem Michael Addition–Cyclization: Exemplification in the Synthesis of Amidine Class BACE1 Inhibitors
Authors: Mateu Natalia , Ciordia Myriam , Delgado Oscar , Sánchez‐Roselló María , Trabanco Andrés A. , Van Gool Michiel , Tresadern Gary , Pérez‐Benito Laura , Fustero Santos
Published: July 2015

The groups of Santos Fustero at the University of Valencia (Spain) and Oscar Delgado at Janssen Research and Development (Spain) have been invited for the front cover of this issue. The image depicts the docking of one of the β‐secretase 1 (BACE1) inhibitors encapsulated in a sketch of the human brain. Read the full text of the article at 10.1002/chem.201501662.
Enhancing treatment and geotechnical stability of oil sands fine tailings using thermo‐sensitive poly(n‐isopropyl acrylamide)
Authors: Li Haihong , Zhou Joe , Chow Ross , Adegoroye Adebukola , Najafi Aref Seyyed
Published: July 2015

A thermo‐sensitive polymer, poly(n‐isopropyl acrylamide) (PNIPAM), was tested in the dewatering (settling, consolidation, and geotechnical stability of shear strength via vane testing) of oil sands fine tailings. The tested samples included <10 and <2 μm (“minus 10” and “minus 2”) size fractions of oil sands mature fine tailings (MFT), and hydrocyclone overflow of fresh oil sands tailings. The performance of PNIPAM was compared with a selected commercial flocculant, a 30 % anionic high molecular weight polyacrylamide (PAM). Test results showed that PNIPAM worked better than PAM in fine solids flocculation, supernatant clarity, sediment consolidation, and geotechnical properties. The superiority of PNIPAM was attributed to its unique features of structural changes with temperature and the combined actions of hydrogen bonding and hydrophobic interaction of PNIPAM with the fine solid particles.
Effects of melatonin on physical fatigue and other symptoms in patients with advanced cancer receiving palliative care: A double‐blind placebo‐controlled crossover trial
Authors: Lund Rasmussen Charlotte , Klee Olsen Marc , Thit Johnsen Anna , Aagaard Petersen Morten , Lindholm Helena , Andersen Line , Villadsen Birgit , Groenvold Mogens , Pedersen Lise
Published: July 2015

BACKGROUND

Patients with advanced cancer often experience fatigue and other symptoms that negatively impact their quality of life. The current trial investigated the effect of melatonin on fatigue and other symptoms in patients with advanced cancer.

METHODS

Patients who were aged ≥18 years, had a histologically confirmed stage IV cancer (TNM Classification), and who reported feeling significantly tired were recruited from the palliative care unit at the study institution. The study was a double‐blind, randomized, placebo‐controlled crossover trial. Patients received 1 week of melatonin at a dose of 20 mg or a placebo orally each night, before crossing over and receiving the opposite treatment for 1 week. Between the 2 periods, a washout period of 2 days was implemented. Outcomes were measured using the Multidimensional Fatigue Inventory (MFI‐20) and The European Organization for Research and Treatment of Cancer Quality of Life Questionnaire. Physical fatigue from the MFI‐20 was the primary outcome. The primary analysis was a complete complier analysis (ie, it included only those patients who had consumed at least 5 capsules per week and who had answered the MFI‐20 on days 1, 7, 10, and 17). Sensitivity analysis using multiple imputations including all randomized patients and all patients completing the intervention were conducted.

RESULTS

A total of 72 patients were randomized. Fifty patients completed the intervention and 44 patients were complete compliers. No significant differences between the placebo and melatonin periods were found for physical fatigue, secondary outcomes, or explorative outcomes.

CONCLUSIONS

In the current study, oral melatonin at a dose of 20 mg was not found to improve fatigue or other symptoms in patients with advanced cancer. Cancer 2015;121:3727–3736. © 2015 American Cancer Society.
Switch from distress to well‐being by strong emotions: Speculations on three clinical vignettes
Authors: Calanchini Carlo
Published: July 2015

Starting from three clinical vignettes representing two mental disorders and different approaches to their treatment, we ask whether and how an unexpected event occurring at a particular time in a person's life could provoke such strong emotions as to determine a sudden transition from a state of severe distress to one of well‐being.

In this transition, we postulate that a major role is played by biological tendencies and brain plasticity under the influence of psychotherapy and positive emotions, emotions—especially trust, the sense of being cared for, and falling in love—that are awakened by openness to novelty and to the Other. Neurobiologically, a sudden improvement could be ascribed to an oxytocinergic action that, combined with dopaminergic circuits, can restore a state of well‐being, safe attachment, and gratification. J. Comp. Neurol. 524:1687–1694, 2016. © 2015 Wiley Periodicals, Inc.
FACE‐IT: A science gateway for food security research
Authors: Montella Raffaele , Kelly David , Xiong Wei , Brizius Alison , Elliott Joshua , Madduri Ravi , Maheshwari Ketan , Porter Cheryl , Vilter Peter , Wilde Michael , Zhang Meng , Foster Ian
Published: July 2015

Progress in sustainability science is hindered by challenges in creating and managing complex data acquisition, processing, simulation, post‐processing, and intercomparison pipelines. To address these challenges, we developed the Framework to Advance Climate, Economic, and Impact Investigations with Information Technology (FACE‐IT) for crop and climate impact assessments. This integrated data processing and simulation framework enables data ingest from geospatial archives; data regridding, aggregation, and other processing prior to simulation; large‐scale climate impact simulations with agricultural and other models, leveraging high‐performance and cloud computing; and post‐processing to produce aggregated yields and ensemble variables needed for statistics, for model intercomparison, and to connect biophysical models to global and regional economic models. FACE‐IT leverages the capabilities of the Globus Galaxies platform to enable the capture of workflows and outputs in well‐defined, reusable, and comparable forms. We describe FACE‐IT and applications within the Agricultural Model Intercomparison and Improvement Project and the Center for Robust Decision‐making on Climate and Energy Policy. Copyright © 2015 John Wiley & Sons, Ltd.
Insight into the Binding Mode of Agonists of the Nicotinic Acetylcholine Receptor from Calculated Electron Densities
Authors: Beck Michael E. , Gutbrod Oliver , Matthiesen Svend
Published: July 2015

Insect nicotinic acetylcholine receptors (nAChRs) are among the most prominent and most economically important insecticide targets. Thus, an understanding of the modes of binding of respective agonists is important for the design of specific compounds with favorable vertebrate profiles. In the case ofnAChRs, the lack of available high‐resolution X‐ray structures leaves theoretical considerations as the only viable option. Starting from classical homology and docking approaches, binding mode hypotheses are created for five agonists of thenAChR, covering insecticides in the main group 4 of the Insecticide Resistance Action Committee (IRAC) mode of action (MoA) classification, namely, neonicotinoids, nicotine, sulfoxaflor, and butenolides. To better understand these binding modes, the topologies of calculated electron densities of small‐model systems are analyzed in the framework of the quantum theory of atoms in molecules. The theoretically obtained modes of binding are very much in line with the biology‐driven IRAC MoA classification of the investigated ligands.
Real‐Time Band‐Selective Homonuclear Proton Decoupling for Improving Sensitivity and Resolution in Phase‐Sensitive J‐Resolved Spectroscopy
Authors: Verma Ajay , Baishya Bikash
Published: July 2015

Real‐time band‐selective homonuclear 1H decoupling during data acquisition of z‐filtered J‐resolved spectroscopy produces 1H‐decoupled 1H NMR spectra and leads to sensitivity enhancement and improved resolution, and thus aids the measurement of J couplings and residual dipolar couplings in crowded regions of 1H NMR spectrum. High quality spectra from peptides, organic molecules, and also from enantiomers dissolved in weakly aligned chiral media are reported.
Vibrational Dephasing in Ionic Liquids as a Signature of Hydrogen Bonding
Authors: Chatzipapadopoulos Susana , Zentel Tobias , Ludwig Ralf , Lütgens Matthias , Lochbrunner Stefan , Kühn Oliver
Published: July 2015

Understanding both structure and dynamics is crucial for producing tailor‐made ionic liquids (ILs). We studied the vibrational and structural dynamics of medium versus weakly hydrogen‐bonded CH groups of the imidazolium ring in ILs of the type [1‐alkyl‐3‐methylimidazolium][bis(trifluoromethanesulfonyl)imide] ([Cnmim][NTf2]), with n=1, 2, and 8, by time‐resolved coherent anti‐Stokes Raman scattering (CARS) and quantum‐classical hybrid (QCH) simulations. From the time series of the CARS spectra, dephasing times were extracted by modeling the full nonlinear response. From the QCH calculations, pure dephasing times were obtained by analyzing the distribution of transition frequencies. Experiments and calculations reveal larger dephasing rates for the vibrational stretching modes of C(2)H compared with the more weakly hydrogen‐bonded C(4,5)H. This finding can be understood in terms of different H‐bonding motifs and the fast interconversion between them. Differences in population relaxation rates are attributed to Fermi resonance interactions.
Primary‐Colored Electrochromism of 1,4‐Phenylenediamines
Authors: Lauw Sherman J. L. , Xu Xiuhui , Webster Richard D.
Published: July 2015

Ten 1,4‐phenylenediamines were studied using electrochemical techniques (voltammetry and controlled potential electrolysis) and UV/Vis spectroscopy under ambient conditions. All compounds demonstrated vibrant color changes upon one‐electron electrochemical oxidation in acetonitrile, with most displaying a primary color (red, green, blue, or yellow) in their oxidized state. The four electrochromes that exhibited the most intense color changes were examined by using a gold micromesh electrode laminated inside a polymer film to determine their electrochromic properties in solution (contrast ratios, chromatic efficiency, and cycle life). Their colored radical cations were also characterized by electron paramagnetic resonance spectroscopy as well as monitored for color retention over a period of 24 hours. Notably, only relatively small potentials were required to initiate the chromatic changes and the oxidized forms of the compounds were long‐lived and unaffected by atmospheric oxygen or moisture.
Negative computer‐imaged ThinPrep Pap test and positive hybrid capture2 HPV co‐testing results: A quality assurance review
Authors: Rao Rema , Molina David , Halligan Allison M. , Vakil Behzad , Alperstein Susan A. , Hoda Rana S.
Published: July 2015

Women ≥30 years of age with negative (−) Pap tests and positive (+) HPV co‐test results have a higher prevalence and cumulative risk of developing high‐grade cervical intraepithelial neoplasia (CIN 2+). Thus, the current management in these women is to repeat co‐test in 12 months or immediate reflex genotyping for HPV16 or HPV 16/18. If genotyping is not an option, timely quality assurance (QA) rescreen of such Pap tests may be a valuable alternative. All ThinPrep Pap tests (TPPT) interpreted as negative for intra epithelial lesion (NILM) or NILM with reactive cellular changes (NILM/RCC) and a (+) high‐risk HPV [Hybrid Capture 2 (HC2), Qiagen, Hilden, Germany] co‐test result over a 45‐month period (10/2009‐06/2013) underwent monthly QA review. The TPPT were screened by the TP Imaging System [TIS, Hologic Inc., Bedford, MA]. Twenty five thousand six hundred and seventy five (18%) NILM and NILM/RCC TPPT of a total of 141,548 TPPT underwent HPV co‐test. HPV test was (+) in 2,300 (8.9%) TPPT cases. HPV (+) cases by age group were <30 years, 486 (21%), and ≥30 years, 1,814 (79%). Upon QA review, 10 cases (0.4%) were reclassified, with significant findings in three cases in ≥30 years. Two cases showed high‐grade squamous intraepithelial lesion (HSIL) on repeat Pap, and one case showed endocervical adenocarcinoma in situ (AIS) on biopsy. Timely QA review of HPV (+) Pap (−) co‐tests is a valuable monitor. Ninety percentage of reclassified cases were in ≥30 age group and 70% were originally signed out by using TIS 22 Field of View (FOV) only. Three reclassified cases had significant findings on follow up (F/U). Diagn. Cytopathol. 2015;43:763–769. © 2015 Wiley Periodicals, Inc.
Evidence of non‐linearity in the association of glycemic control with influenza/pneumonia mortality: a study of 19 000 adults from the US general population
Authors: Breitling Lutz P.
Published: July 2015

Background

Diabetes is a major public health problem and thought to be a risk factor for infectious diseases, but pertinent epidemiological evidence is limited. This study aimed to analyse the associations of diabetes, disease duration and glycated haemoglobin levels (HbA1c) with infectious diseases mortality in the general population, including the investigation of potential non‐linear relationships.

Methods

An observational, prospective study of 19 783 subjects included in the Third National Health and Nutrition Examination Survey, representing the adult non‐institutionalized population of the United States of America, was conducted. The analysis was done by multiple Cox regression and restricted cubic spline modelling.

Results

Self‐reported diabetes and diabetes duration were not significantly associated with the outcomes. However, there was evidence for a non‐linear association of HbA1c with mortality from influenza, pneumonia or other acute lower respiratory infections. Spline regression suggested a roughly doubled risk of mortality beyond an HbA1c of 6.5% (48 mmol/mol) in reference to 5.2% (33 mmol/mol).

Conclusions

Future studies on diabetes and infections should adequately address potential non‐linearity, which may be necessary to better understand and characterize more precisely the relationship of diabetes with infectious diseases. Copyright © 2015 John Wiley & Sons, Ltd.
Developmental control of transcriptional and proliferative potency during the evolutionary emergence of animals
Authors: Arenas‐Mena Cesar , Coffman James A.
Published: July 2015

It is proposed that the evolution of complex animals required repressive genetic mechanisms for controlling the transcriptional and proliferative potency of cells. Unicellular organisms are transcriptionally potent, able to express their full genetic complement as the need arises through their life cycle, whereas differentiated cells of multicellular organisms can only express a fraction of their genomic potential. Likewise, whereas cell proliferation in unicellular organisms is primarily limited by nutrient availability, cell proliferation in multicellular organisms is developmentally regulated. Repressive genetic controls limiting the potency of cells at the end of ontogeny would have stabilized the gene expression states of differentiated cells and prevented disruptive proliferation, allowing the emergence of diverse cell types and functional shapes. We propose that distal cis‐regulatory elements represent the primary innovations that set the stage for the evolution of developmental gene regulatory networks and the repressive control of key multipotency and cell‐cycle control genes. The testable prediction of this model is that the genomes of extant animals, unlike those of our unicellular relatives, encode gene regulatory circuits dedicated to the developmental control of transcriptional and proliferative potency. Developmental Dynamics 244:1193–1201, 2015. © 2015 Wiley Periodicals, Inc.
Spatial variation in nutrient dynamics among five different peatland types in the Alberta oil sands region
Authors: Wood Meagan E. , Macrae Merrin L. , Strack Maria , Price Jonathan S. , Osko Terrance J. , Petrone Richard M.
Published: July 2015

Wetlands are found extensively throughout the Western Boreal Plain, a region under pressure because of disturbance by the oil and gas industries. To understand how wetland systems may respond to disturbance and set targets for reclamation efforts, it is necessary to understand natural variability in nutrient dynamics in the landscape. The purpose of this study was to characterize spatial variability in peatland nutrient (nitrogen, N, and phosphorus, P) dynamics in the Athabasca Oil Sands (AOS) region. N and P availability and net mineralization rates in the upper 10 cm layer of peat were examined during the peak growing season in five peatlands that fell along an apparent moisture gradient. N and P dynamics within and among the sites were related to water table position, peat moisture content and temperature. Phosphorus supply rates and total inorganic N pools and supply rates were generally elevated under wetter conditions, whereas nitrate (NO3−) pools and supply rates and P pools did not vary along a moisture gradient. In general, net immobilization was observed at the wetter sites where nutrient pools were elevated and net mineralization was observed at drier sites where nutrient pools were lower. Nutrient transformation rates were most strongly driven by warmer temperatures. Nutrient availability and immobilization rates were anomalously high at one peatland (a disturbed fen with a semi‐permanent road and decommissioned well pads). We suggest that reclamation and management practices should focus on regulating peatland hydrologic conditions, optimizing these for the most desirable nutrient levels for vegetation growth. Copyright © 2015 John Wiley & Sons, Ltd.
Non‐thrombotic fatal pulmonary embolism with a ‘rule‐out’ CT scan
Authors: Beug Daniel , Friesecke Sigrun , Felix Stephan B. , Empen Klaus
Published: July 2015

We report on a 36‐year‐old woman suffering from metastasized breast cancer and severe dyspnoea owing to right heart failure. Symptoms and findings were highly suggestive of pulmonary embolism. In rare cases, pulmonary embolism is caused not by migration of venous thrombi but by emboli of other origin. Patients with cancer can suffer from non‐thrombotic pulmonary embolism, either by (macroscopic) embolization of tumour mass or by microembolism also known as microscopic tumour microangiopathy. In patients with cancer with clinical presentation highly suggestive of pulmonary embolism, with echocardiographic findings confirming right ventricular dysfunction, and with negative CT angiography, pulmonary tumour microembolism should be considered as possible diagnosis.
Ruthenium Imidazophenanthrolinium Complexes with Prolonged Excited‐State Lifetimes
Authors: Staehle Robert , Reichardt Christian , Popp Jürgen , Sorsche Dieter , Petermann Lydia , Kastner Katharina , Streb Carsten , Dietzek Benjamin , Rau Sven
Published: July 2015

A series of ruthenium polypyridyl complexes [Ru(tbbpy)3][PF6]2 (0, tbbpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine), [Ru(tbbpy)2(bbip)][PF6]3 {1, (bbip)Br = 1,3‐(bisbenzyl)‐1H‐imidazo[4,5‐f][1,10]phenanthrolinium bromide}, [Ru(tbbpy)(bbip)2][PF6]4 (2), and [Ru(bbip)3][PF6]5 (3) were synthesized. The new complexes 2 and 3 were fully characterized, and their X‐ray crystal structures, absorption and emission spectra, quantum yields of emission, and cyclic voltammograms were determined. Within this series, a trend towards increased lifetime and quantum yields of emission can be observed, especially in the presence of oxygen. The location of the first excited state on the imidazophenanthrolinium ligands has been elucidated by resonance Raman spectroscopy of 1 and 3, which revealed that the energy of the π* orbitals of the bbip ligands is lower than that of the π* orbitals of the tbbpy ligand.
Understanding and Tuning Bioinorganic Interfaces for the Design of Bionanocomposites
Authors: Voisin Hugo , Aimé Carole , Coradin Thibaud
Published: July 2015

Interactions between biological molecules and inorganic species are of tremendous importance in nature. Attempts to create bionanocomposites associating nanoscale inorganic objects with biomolecules face major challenges with regard to controlling their mutual reactivity and preserving their intrinsic properties. This review describes the interactions arising between polyoxometallates or silica particles and biomolecules – including proteins, polysaccharides, lipids and nucleic acids – that depend on physicochemical conditions. It shows that chemical modification of the inorganic and/or bio‐organic partner allows fine‐tuning of their interface. The specific properties of these bionanocomposites are illustrated, with emphasis on their potential in biotechnology and biomedicine. This field contributes to a better understanding of the “biochemistry of solids” and offers an almost unlimited playground for the elaboration of new materials that combine molecular biodiversity with chemistry in its many facets.
Si(OCH2Fc)4: Synthesis, Electrochemical Behavior, and Twin Polymerization
Authors: Schliebe Christian , Pfaff Ulrike , Gemming Thomas , Lochenie Charles , Weber Birgit , Lang Heinrich
Published: July 2015

The preparation and twin polymerization of the twin monomer Si(OCH2Fc)4 [Fc = Fe(η5‐C5H4)(η5‐C5H5)] (2) by the reaction of FcCH2OH (1) with SiCl4 in the presence of pyridine was explored. The electronic properties of 2 were investigated by cyclic voltammetry, square‐wave voltammetry, and UV/Vis/near‐IR spectroelectrochemistry, which showed a redox separation caused by electrostatic repulsion. Thermally induced condensation of 2 is characteristic, as evidenced by differential scanning calorimetry (DSC) and thermogravimetry coupled mass spectrometry (TG–MS). Upon heating 2 to 210 °C, twin polymerization occurred and a hybrid material was formed that showed similarities with known systems derived from 2,2′‐spirobi[4H‐1,3,2‐benzodioxasiline] (SBS), such as the nanopatterning of the formed silicon dioxide, which is characteristic for twin polymerization. Electron microscopy of this material revealed the absence of typical microstructuring found for other twin polymers, and hence, the herein presented system can be characterized as a borderline system if compared to known twin monomers such as SBS. The copolymerization of 2 and SBS afforded a hybrid material from which porous carbon or silica materials containing iron oxide nanoparticles could be obtained. The oxidation state of the incorporated particles was examined by Mössbauer experiments, which confirmed that only FeIII was incorporated within the porous carbon and silica materials, respectively. The preparation of iron oxide containing porous carbon capsules was achieved by applying a mixture of 2 and SBS to silicon dioxide spheres (d = 200 nm). After twin polymerization and carbonization, porous carbon capsules with incorporated iron oxide nanostructures were obtained.
Cobalt(I) and Nickel(II) Complexes of Bis(1,3‐diphosphacyclobutadiene) Sandwich Anions
Authors: Rödl Christian , Wolf Robert
Published: July 2015

Complexes [(C4Me4)Co(CO)2{Co(P2C2tBu2)2}] (1, C4Me4 = tetramethylcyclobutadiene) and [CpNi{Co(P2C2tBu2)2}(PPh3)] (2, Cp = cyclopentadienyl) were synthesized by transmetalating [Tl(thf)2{Co(P2C2tBu2)2}] with [(C4Me4)Co(CO)2I] and [CpNiBr(PPh3)]. Compounds 1 and 2 were fully characterized by X‐ray crystallography, multinuclear NMR, UV/Vis, and IR spectroscopy, and elemental analysis. Their molecular structures show σ‐coordination of one phosphorus atom of the [Co(P2C2tBu2)2]– anion to the second metal atom (cobalt or nickel). Time‐dependent density functional theory (TD‐DFT) calculations were applied to gain insight into the electronic structures and the nature of the electronic transitions observed in the UV/Vis spectra. Cyclic voltammetry studies revealed the similar redox behavior of 1 and 2, which are reversibly oxidized to the corresponding monocations 1+ and 2+ with retention of the dinuclear structures. The cyclic voltammograms furthermore show that 1 and 2 decompose upon reduction with cleavage of the dinuclear structures into the free [Co(P2C2tBu2)2]– anion and further uncharacterized products.
Infant formula interface and fat source impact on neonatal digestion and gut microbiota
Authors: Bourlieu Claire , Bouzerzour Karima , Ferret‐Bernard Stéphanie , Bourgot Cindy Le , Chever Sophie , Ménard Olivia , Deglaire Amélie , Cuinet Isabelle , Ruyet Pascale Le , Bonhomme Cécile , Dupont Didier , Huërou‐Luron Isabelle Le
Published: July 2015

Human milk is generally recognized as the gold standard in neonatal nutrition. The structure and composition of human milk are better mimicked in infant formulas that include cow's milk lipids and milk fat membrane extracts, which could also improve physiological properties. Nevertheless, very few infant formulas use cow's milk lipids that are more expensive than vegetable lipids. The potential impact of milk lipid structure and composition on neonatal digestive hydrolysis, intestinal physiology, and gut microbiota was recently underlined by several scientific teams. In this context, the purpose of the present review was to summarize the specificity of composition and structure of human milk and to highlight the recent results on the modulation of infant formula interfacial composition and fat source on neonatal digestive hydrolysis, intestinal physiology, and gut microbiota. More specifically, the interfacial composition of model emulsions stabilized with milk polar lipids will be unraveled as well as the addition of apolar milk fat extracts in replacement to vegetable lipids in infant formulas. The impact of partially replacing vegetable lipids by milk lipids stabilized by milk fat membranes was investigated in the piglets. This replacement influenced the neonatal intestinal physiology through the release of immune‐modulatory lipids, the modulation of proteolysis, and the modification of gut microbiota.

Practical applications: The potential development of infant formulas including cow's milk lipid fractions with a structure closer to human milk is discussed. These more biomimetic formulas should result in enhanced nutritional benefits concerning neonatal digestive hydrolysis, physiology, and gut microbiota development.

The structure and composition of human milk are better mimicked in infant formulas that include cow's milk lipids and milk fat membrane extracts, although very few infant formulas use cow's milk lipids as it is more expensive than vegetable lipids. The potential impacts of milk lipid structure and composition on neonatal digestive hydrolysis, intestinal physiology, and gut microbiota are recently underlined by several scientific teams and are summarized in this present review.
An Electrochemical Sensor for the Simultaneous Determination of Paracetamol and Codeine Using a Glassy Carbon Electrode Modified with Nickel Oxide Nanoparticles and Carbon Black
Authors: Batista Deroco Patrícia , Campanhã Vicentini Fernando , Fatibello‐Filho Orlando
Published: July 2015

In this work, a simple and highly selective voltammetric method was developed for the simultaneous determination of paracetamol (PCT) and codeine (COD) in pharmaceuticals and human body fluids employing a glassy carbon electrode modified with carbon black (CB) and nickel oxide nanoparticles (NiONPs) within a dihexadecylphosphate (DHP) film. Using square‐wave voltammetry (SWV), a separation of ca. 550 mV between the oxidation peak potentials of PCT and COD was obtained. The simultaneous determination of PCT and COD presented a linear concentration range from 3.0 to 47.8 µmol L−1 for PCT and from 0.83 to 38.3 µmol L−1 for COD.
Fabrication of a Nanostructure Based Electrochemical Sensor for Voltammetric Determination of Epinephrine, Uric Acid and Folic Acid
Authors: Mahmoudi Moghaddam Hadi , Beitollahi Hadi , Tajik Somayeh , Soltani Hossein
Published: July 2015

A carbon paste electrode (CPE) was modified by incorporation of graphene nano sheets and a ferrocene derivative. The modified electrode showed an excellent electrocatalytic effect on the oxidation of epinephrine. In phosphate buffer solution (PBS) of pH 7.0, the oxidation current increased linearly with concentration of epinephrine in the range of 0.05–550.0 µM and a detection limit (3σ) 27.0 nM was obtained for epinephrine. Then the modified electrode was used to determine epinephrine in an excess of uric acid and folic acid by SWV.
Acidic and Basic Functionalized Carbon Nanomaterials as Electrical Bridges in Enzyme Loaded Chitosan/Poly(styrene sulfonate) Self‐Assembled Layer‐by‐Layer Glucose Biosensors
Authors: David Melinda , Barsan Madalina M. , Florescu Monica , Brett Christopher M. A.
Published: July 2015

Glucose oxidase (GOx) was incorporated in a self‐assembled multilayer modified gold electrode, based on electrostatic interaction between positively charged chitosan polymer, containing GOx, and negatively charged poly(styrene sulfonate). Good electronic communication between electrode and enzyme was ensured by carbon nanomaterials (CN), graphene (G) or carbon nanotubes (CNT) functionalised in either HNO3 or KOH, immobilized together with the enzyme. Cyclic voltammetry and electrochemical impedance spectroscopy enabled identification of the glucose biosensor assemblies with the best functionalized CN, KOH_G and HNO3_CNT, confirmed by fixed potential amperometry at −0.3 V vs. Ag/AgCl, these glucose biosensors exhibiting the highest sensitivities and lowest detection limits.
Assessment of Oxidative Stress in Patients with an Isolated Traumatic Brain Injury Using Disposable Electrochemical Test Strips
Authors: Rael Leonard T. , Bar‐Or Raphael , Kelly Michael T. , Carrick Matthew M. , Bar‐Or David
Published: July 2015

The barriers to using plasma redox potential as a measure of oxidative stress in patients are the use of specialized equipment, necessity of sterilization between tests, and inconsistent electrode surfaces and cell geometry. These problems are resolved using disposable test strips with built in electrochemical cells. Measuring the electrode potential at a small current yields a stable value that is ∼50 mV higher for isolated traumatic brain injury (ITBI) patients than for healthy individuals. Even with natural variations within blood chemistry, this simple method may be clinically useful for assessing the degree of oxidative stress and injury severity in ITBI patients.
Simultaneous and Selective Detection of Environment Hazardous Metals in Water Samples by Using Flower and Christmas Tree Like Cerium Hexacyanoferrate Modified Electrodes
Authors: Devadas Balamurugan , Sivakumar Mani , Chen Shen‐Ming , Rajkumar Muniyandi , Hu Chi‐Chang
Published: July 2015

We report facile, template‐free, surfactant‐less flower and Christmas tree‐like cerium hexacyanoferrate (CeHCF) modified electrodes for simultaneous measurement of environmentally hazardous metals. The hierarchical growth of CeHCF on electrode surface was controlled by electrodeposition time at constant potential. This CeHCF modified electrode exhibits a prominent electrocatalytic activity towards detection of heavy metal ions such as cadmium (Cd), copper (Cu), lead (Pb) and mercury (Hg). The peaks are separated well at CeHCF modified electrode. Well separated peaks for the detection of these heavy metals in lake and tap water samples indicating CeHCF modified electrode as successful electrode for the reported sensor.
Adsorptive Cathodic Stripping Voltammetric Method for Determination of Gallium Using an In Situ Plated Lead Film Electrode
Authors: Grabarczyk Malgorzata , Wasąg Joanna
Published: July 2015

The in situ plated lead film electrode was proposed for the first time for adsorptive stripping voltammetric determination of gallium in water samples. The method was based on simultaneous lead film formation and Ga(III)‐cupferron complex preconcentration at −0.7 V and its cathodic stripping during the potential scan. The composition of the supporting electrolyte, cupferron concentration, conditions of lead film formation, potential and time of accumulation were studied in detail. Under optimum conditions the limit of detection was 3.8×10−9 mol L−1. The proposed procedure was validated in the course of Ga(III) determination in waste water certified reference materials.
Nanocellulose/Carbon Nanoparticles Nanocomposite Film Modified Electrode for Durable and Sensitive Electrochemical Determination of Metoclopramide
Authors: Shahrokhian Saeed , Naderi Leila , Ghalkhani Masoumeh
Published: July 2015

A novel electrochemical sensor based on nanocellulose‐carbon nanoparticles (NC‐CNPs) nanocomposite film modified glassy carbon electrode (GCE) is developed for the analysis of metoclopramide (MCP). Atomic force microscopy, scanning electron microscopy and electrochemical impedance spectroscopy were used to characterize the roughness, surface morphology and performance of the deposited modifier film on GCE. SEM image demonstrated that modifier nanoparticles are uniformly deposited on GCE, with an average size of less than 50 nm. The electrochemical behavior of MCP and its oxidation product is studied using linear sweep and cyclic voltammetry over a wide pH range on NC‐CNPs modified glassy carbon electrode. The results revealed that the oxidation of MCP is an irreversible and pH‐dependent process that proceeds in an adsorption‐controlled mechanism and results in the formation of a main oxidation product, which adsorbs on the surface of NC‐CNPs/ GCE. The modified electrode showed a distinctive anodic response towards MCP with a considerable enhancement (49 fold) compared to the bare GCE. Under the optimized conditions, the modified electrode exhibited a wide linear dynamic range of 0.06–2.00 µM with a detection limit of 6 nM for the voltammetric determination of MCP. The prepared modified electrode showed several advantages such as simple preparation method, high stability, reproducibility, and repetitive usability. The modified electrode is successfully applied for the accurate determination of trace amounts of MCP in pharmaceutical and clinical preparations.
A Novel Electroactive Polymer for pH‐independent Oxygen Sensing
Authors: Ng Shu Rui , Pang Hongchang , Chen Peng , Li Chang Ming , O'Hare Danny
Published: July 2015

Methylene blue (MB+) and pyrrole were copolymerised to electrodeposit a novel electroactive polymer on a Au electrode which was assessed for O2 sensing. The electroactive polymer exhibits diffusion‐limited behaviour and an electrochemical, followed by catalytic (EC′) mechanism in the presence of dissolved O2. Notably, it is pH‐insensitive in both N2‐purged and air‐equilibrated phosphate buffered saline (PBS) from pH 4 to 8. It is stable over 18 days, possesses a good sensitivity of 256.335 µA mM−1 cm−2, wide linear range of 15 µM to 285 µM and detection limit of 1.47 µM (S/N=3) for dissolved O2. It is highly promising for use in biological investigations where pH fluctuations are expected.
Flame retardancy in fabric consisting of cellulosic fiber and modacrylic fiber containing fine‐grained MoO3 particles
Authors: Tanaka Takeshi , Terakado Osamu , Hirasawa Masahiro
Published: July 2015

Flame retardancy of fabrics consisting of modacrylic fiber containing with various dispersed metal compounds and cellulosic fiber has been investigated by means of flame test (ISO15025 procedure A) and limiting oxygen index (LOI). It has been found that excellent flame retardancy is achieved by fine‐grained MoO3 particles. The afterflame time in flame test and the LOI value are improved with decreasing particle size of MoO3. The flame retardancy of MoO3 (particle size; 0.1 µm) is comparable to that of Sb2O3. On the other hand, significant improvement in flame retardancy is not observed for other metal compounds although some metal oxides and a hydroxide in the present study are known as flame retardant or smoke suppressing agent in halogen containing polymer in previous studies. In order to clarify the mechanism of the observed flame retardancy by the addition of fine‐grained MoO3, we have carried out X‐ray fluorescence spectrometry (XRF) measurement of the fabric specimen after the flame test and thermogravimetric analysis (TGA) of various types of samples. These analytical data indicated that MoO3 works as halogen synergist in solid phase and the char of modacrylic fiber formed by addition of MoO3 suppresses decomposition of the cotton blended in the fabric in the range of the ignition temperature. Copyright © 2015 John Wiley & Sons, Ltd.
Allometric relations between fluvial impulse and morphometric parameters of floodplain lakes
Authors: Ferencz Beata , Dawidek Jarosław
Published: July 2015

The general role of river water input in shaping the basic morphometric parameters of floodplain lakes has been previously investigated. However, the process has not been quantitatively described in detail. This study is the first attempt in the literature to determine the allometric relation between fluvial impulse, expressed as Fluvial Connectivity Quotient, and morphometric parameters of six floodplain lakes of Bug River valley in the period 1952–2014. This relationship is given by Y = aXb, from which the value of b exponent was analysed to determine the strength of the allometric relation. Extreme values of allometric compounds during the time period under study ranged from 5.99 to −4.91. Volume was the morphometric parameter showing the highest variability in all the lakes. General similarity in allometric relations was observed in the lakes under study. During analysis, no long‐term trends were observed in the relationship between the Fluvial Connectivity Quotient and morphometric parameters. The results obtained show that fluvial impulse was the factor determining the variability of morphometric parameters of the lakes. Direct catchments topography of lake has periodically (during limnophase periods) played a significant role in shaping the morphometry of floodplain lakes. The most stable allometric relations occurred in a confluent lake, with a low limnological effective rise value and consequently, relatively long potamophase periods.Copyright © 2015 John Wiley & Sons, Ltd.
Using eye gaze to identify reinforcers for individuals with severe multiple disabilities
Authors: Cannella‐Malone Helen I. , Sabielny Linsey M. , Tullis Christopher A.
Published: July 2015

The purpose of this study was to replicate Fleming et al. (2010) by examining the use of eye gaze in identifying reinforcers for 3 individuals with severe multiple disabilities. Preference was measured in a paired‐choice stimulus preference assessment using duration of eye gaze to determine stimulus selection. A subsequent reinforcer assessment used a reversal design to test the reinforcing effects of the high‐ and low‐preference stimuli. The results replicated Fleming et al., indicating that using eye gaze as a selection method successfully identified reinforcing stimuli.
A comparison of differential reinforcement procedures with children with autism
Authors: Boudreau Brittany A. , Vladescu Jason C. , Kodak Tiffany M. , Argott Paul J. , Kisamore April N.
Published: July 2015

The current evaluation compared the effects of 2 differential reinforcement arrangements and a nondifferential reinforcement arrangement on the acquisition of tacts for 3 children with autism. Participants learned in all reinforcement‐based conditions, and we discuss areas for future research in light of these findings and potential limitations.
Experimental and Theoretical Charge Density Study on Di‐2‐pyrazylamine (Hdpza) Molecule in Crystal
Authors: Wu Lai‐Chin , Lee Gene‐Hsiang
Published: July 2015

Electron density distribution of Di‐2‐pyrazylamine (Hdpza) is studied both by single‐crystal X‐ray diffraction method at 100K and theoretical calculation. Structural determination reveals that Hdpza molecules crystalize in a syn‐anti conformation with an intramolecular CHN hydrogen bond between two pyrazine rings and then gather together via two intermolecular NHN and CHN hydrogen interaction and ππ stacking interaction between pyrazine rings. Charge density analysis is made in terms of deformation density (Δπ), Laplacian distribution and topological analysis of total electron density based on multipole model and theoretical calculation. The agreement between experiment and theory is good. The topological properties at bond critical points of CC and CN bonds reveal a covalent bond character, and those of intermolecular interactions, such as hydrogen bonds and ππ stacking interactions, reveal a closed‐shell interaction. The potential energy curve of Hdpza molecule shows that the syn‐anti conformation is the most stable one (global minima) than the other two of syn‐syn and anti‐anti conformations.
Anticandida Agents from a Tanzanian Plant Albizia anthelmintica
Authors: Runyoro Deborah K. B. , Joseph Cosam C. , Ngassapa Olipa D. , Darokar Mahendra P. , Srivastava Santosh K. , Matee Mecky I. N. , Wright Colin W.
Published: July 2015

Candidiasis is one of the most frequent opportunistic infections in individuals with severe immunosupression and further development of resistance against the available antifungal drugs has created an alarming situation. This requires intensive drug discovery to develop new, more effective, affordable and accessible antifungal agents possessing novel modes of action. Albizia anthelmintica, which is ethno medically used to treat vaginal candidiasis in the Morogoro and coastal regions of Tanzania, on activity guided fractionation and subsequent purification resulted in the isolation and characterization of an isomer of methyl cyclitol (1) and six echinocystic acid saponins (2–7). Saponins 6 and 7 are new and being reported for the first time from nature. Among all the isolated compounds, 3‐O‐[α‐L‐arabinopyranosyl (1→2)][α‐L‐arabinopyranosyl (1→6)]‐2‐acetamido‐2‐deoxy‐β‐D‐glucopyranosyl echinocystic acid (4), 3‐O‐[α‐L‐arabinopyranosyl (1→2)] [α‐L‐arabinopyranosyl (1→6)]‐2‐amino‐2‐deoxy‐β‐D‐glucopyranosyl echinocystic acid (6) and 3‐O‐[β‐D‐glucopyranosyl (1→3)] [α‐L‐arabinopyranosyl (1→2)] [α‐L‐arabinopyranosyl (1→6)]‐2‐amino‐2‐deoxy‐β‐D‐glucopyranosyl echinocystic acid (7) and their combinations were active against the various strains of C. albicans with MICs ranging from 12.5 to 125 μg/ml.
Synthesis and Biological Activities of 6‐Hydroxyaurone Derivatives
Authors: Bao Yong‐Tuan , Zhang Min , Li Ting , Xiao Hui‐Feng , Zhao Ting , Xu Xiao‐Hua , Yang Liu‐Qing
Published: July 2015

A series of 6‐hydroxyaurone derivatives were synthesized in satisfactory yields and characterized by IR, 1H NMR, 13C NMR, and HRMS or elemental analysis. The structure of compound 3e was further confirmed by X‐ray crystal analysis. Bioassay results indicated that some of the target compounds displayed moderate herbicidal activity against the dicotyledonous plant Brassica campestris L. at 100 µg·mL−1, and some compounds also showed significant antiproliferative activity against tumor cell lines Hela, HepG‐2, and MCF‐7.
Diversity and composition of the bacterial community in Amphioxus feces
Authors: Pan Minming , Yuan Dongjuan , Chen Shangwu , Xu Anlong
Published: July 2015

Amphioxus is a typical filter feeder animal and is confronted with a complex bacterial community in the seawater of its habitat. It has evolved a strong innate immune system to cope with the external bacterial stimulation, however, the ecological system of the bacterial community in Amphioxus remains unknown. Through massive parallel 16S rRNA gene tag pyrosequencing, the investigation indicated that the composition of wild and lab‐cultured Amphioxus fecal bacteria was complex with more than 85,000 sequence tags being assigned to 12/13 phyla. The bacterial diversity between the two fecal samples was similar according to OTU richness of V4 tag, Chao1 index, Shannon index and Rarefaction curves, however, the most prominent bacteria in wild feces were genera Pseudoalteromonas (gamma Proteobacteria) and Arcobacter (epsilon Proteobacteria); the highly abundant bacteria in lab‐cultured feces were other groups, including Leisingera, Phaeobacter (alpha Proteobacteria), and Vibrio (gamma Proteobacteria). Such difference indicates the complex fecal bacteria with the potential for multi‐stability. The bacteria of habitat with 28 assigned phyla had the higher bacterial diversity and species richness than both fecal bacteria. Shared bacteria between wild feces and its habitat reached to approximately 90% (153/169 genera) and 28% (153/548 genera), respectively. As speculative, the less diversity of both fecal bacteria compared to its habitat partly because Amphioxus lives buried and the feces will ultimately end up in the sediment. Therefore, our study comprehensively investigates the complex bacterial community of Amphioxus and provides evidence for understanding the relationship of this basal chordate with the environment.