bluuebunny/crossref_metadata_2025 huggingface dataset:
Regioselective Amine–Borane Cyclization: Towards the Synthesis of 1,2‐BN‐3‐Cyclohexene by Copper‐Assisted Triazole/Gold Catalysis
Authors: Motika Stephen E. , Wang Qiaoyi , Akhmedov Novruz G. , Wojtas Lukasz , Shi Xiaodong
Published: August 2016

The combination of triazole/gold (TA‐Au) and Cu(OTf)2 is identified as the optimal catalytic system for promoting intramolecular hydroboration for the synthesis of a six‐membered cyclic amine–borane. Excellent yields (up to 95 %) and regioselectivities (5‐exo vs. 6‐endo) were achieved through catalyst control and sequential dilution. Good functional‐group tolerance was attained, thus allowing the preparation of highly functionalized cyclic amine–borane substrates, which could not be achieved using other methods. Deuterium‐labeling studies support the involvement of a hydride addition to a gold‐activated alkyne with subsequent C−B bond formation.
A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene
Authors: Ohsato Takuto , Okuno Yuri , Ishida Shintaro , Iwamoto Takeaki , Lee Ka‐Ho , Lin Zhenyang , Yamashita Makoto , Nozaki Kyoko
Published: August 2016

A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.
Synthese von Strophasterol A – einer Biosynthesevermutung und inhärenter Reaktivität folgend
Authors: Heinze Robert C. , Lentz Dieter , Heretsch Philipp
Published: August 2016

Die Synthese von Strophasterol A, einem Moderator des Stresses des endoplasmatischen Retikulums (ER‐Stress) in der Alzheimer‐Krankheit und erstem Vertreter einer neuartigen Klasse von Secosterolen, gelang unter Anwendung eines Schrittes aus dessen vermuteter Biosynthese sowie zweier C‐H‐Oxidationen. Die Analyse der Intermediate unter Gesichtspunkten ihrer inhärenten Reaktivität ermöglichte es weiterhin, eine neuartige Synthese eines α‐Chlor‐γ‐hydroxy‐δ‐ketoenons sowie seine Verwendung in einer vinylogen α‐Ketol‐Umlagerung hin zu einer δ‐Ketocarbonsäure zu identifizieren.
Excited States of Nucleic Acids Probed by Proton Relaxation Dispersion NMR Spectroscopy
Authors: Juen Michael Andreas , Wunderlich Christoph Hermann , Nußbaumer Felix , Tollinger Martin , Kontaxis Georg , Konrat Robert , Hansen D. Flemming , Kreutz Christoph
Published: August 2016

In this work an improved stable isotope labeling protocol for nucleic acids is introduced. The novel building blocks eliminate/minimize homonuclear 13C and 1H scalar couplings thus allowing proton relaxation dispersion (RD) experiments to report accurately on the chemical exchange of nucleic acids. Using site‐specific 2H and 13C labeling, spin topologies are introduced into DNA and RNA that make 1H relaxation dispersion experiments applicable in a straightforward manner. The novel RNA/DNA building blocks were successfully incorporated into two nucleic acids. The A‐site RNA was previously shown to undergo a two site exchange process in the micro‐ to millisecond time regime. Using proton relaxation dispersion experiments the exchange parameters determined earlier could be recapitulated, thus validating the proposed approach. We further investigated the dynamics of the cTAR DNA, a DNA transcript that is involved in the viral replication cycle of HIV‐1. Again, an exchange process could be characterized and quantified. This shows the general applicablility of the novel labeling scheme for 1H RD experiments of nucleic acids.
Cooperative Self‐Assembly of a Quaternary Complex Formed by Two Cucurbit[7]uril Hosts, Cyclobis(paraquat‐p‐phenylene), and a “Designer” Guest
Authors: Tootoonchi Mohammad Hossein , Sharma Gaurav , Calles Jonathan , Prabhakar Rajeev , Kaifer Angel E.
Published: August 2016

The self‐assembly in aqueous solution of the well‐known cyclophane, cyclobis(paraquat‐p‐phenylene) (BB4+), and two cucurbit[7]uril (CB7) hosts around a simple hydroquinol‐based, diamine guest (GH22+) was investigated by 1H NMR and electronic absorption spectroscopies, electrospray mass spectrometry and DFT computations. The formation of a quaternary supramolecular assembly [GH22+⋅BB4+⋅ (CB7)2] was shown to be a very efficient process, which takes place not only because of the attractive forces between each of the hosts and the guest, but also because of the lateral interactions between the hosts in the final assembly. This complementary set of attractive interactions results in clear cooperative binding effects that help overcome the entropic barriers for multiple component assembly.
Precise Formation of a Hollow Carbon Nitride Structure with a Janus Surface To Promote Water Splitting by Photoredox Catalysis
Authors: Zheng Dandan , Cao Xu‐Ning , Wang Xinchen
Published: August 2016

The precise modification of redox species on the inner and outer surfaces of hollow nanostructures is relevant in catalysis, surface science, and nanotechnology, but has proven difficult to achieve. Herein, we develop a facile approach to specifically fabricate Pt and Co3O4 nanoparticles (NPs) onto the interior and exterior surface of hollow carbon nitride spheres (HCNS), respectively, to promote the surface redox functions of the polymer semiconductors. The photocatalytic water splitting activities of HCNS with spatially separated oxidation and reduction centers at their nanodomains were enhanced. The origin of the enhanced activity was attributed to the spatially separated reactive sites for the evolution of H2 and O2 and also to the unidirectional migration of the electron and hole on the Janus surfaces, thereby preventing the unwanted reverse reaction of water splitting and decreasing charge recombination.
Darwin's Warm Little Pond: A One‐Pot Reaction for Prebiotic Phosphorylation and the Mobilization of Phosphate from Minerals in a Urea‐Based Solvent
Authors: Burcar Bradley , Pasek Matthew , Gull Maheen , Cafferty Brian J. , Velasco Francisco , Hud Nicholas V. , Menor‐Salván César
Published: August 2016

The poor reactivity of insoluble phosphates, such as apatite‐group minerals, has been a long‐appreciated obstacle for proposed models of prebiotic organophosphate formation. This obstacle presents a significant challenge to the nascent development of an RNA world and other models for the origins of life on Earth. Herein, we demonstrate that a scenario based on the formation of a urea/ammonium formate/water (UAFW) eutectic solution leads to an increase in phosphorylation when compared to urea alone for phosphate sources of varying solubility. In addition, under evaporative conditions and in the presence of MgSO4, the UAFW eutectic mobilizes the phosphate sequestered in water‐insoluble hydroxyapatite, giving rise to a marked increase in phosphorylation. These results suggest that the prebiotic concentrations of urea in a geologically plausible evaporitic environment could solve the problem of organic phosphorylation on a prebiotic Earth.
Which Metals are Green for Catalysis? Comparison of the Toxicities of Ni, Cu, Fe, Pd, Pt, Rh, and Au Salts
Authors: Egorova Ksenia S. , Ananikov Valentine P.
Published: August 2016

Environmental profiles for the selected metals were compiled on the basis of available data on their biological activities. Analysis of the profiles suggests that the concept of toxic heavy metals and safe nontoxic alternatives based on lighter metals should be re‐evaluated. Comparison of the toxicological data indicates that palladium, platinum, and gold compounds, often considered heavy and toxic, may in fact be not so dangerous, whereas complexes of nickel and copper, typically assumed to be green and sustainable alternatives, may possess significant toxicities, which is also greatly affected by the solubility in water and biological fluids. It appears that the development of new catalysts and novel applications should not rely on the existing assumptions concerning toxicity/nontoxicity. Overall, the available experimental data seem insufficient for accurate evaluation of biological activity of these metals and its modulation by the ligands. Without dedicated experimental measurements for particular metal/ligand frameworks, toxicity should not be used as a “selling point” when describing new catalysts.
Expression of TLR2/4 on Epididymal Spermatozoa of the Chinese Soft‐Shelled Turtle Pelodiscus sinensis During the Hibernation Season
Authors: Hu Lisi , Li Quanfu , Yang Ping , Gandahi Jameel A. , Arain Tamseel S. , Le Yuan , Zhang Qian , Liu Tengfei , Y. Waqas Muhammad , Ahmad Nisar , Liu Yi , Chen Qiusheng
Published: August 2016

Spermatozoa are known to be stored in the epididymis of the Chinese soft‐shelled turtle Pelodiscus sinensis for long periods during hibernation, but the mechanism that underlies the sperm storage is poorly understood. This study was carried out to confirm the presence of TLR2/4 (Toll‐like receptor 2/4) in epididymal spermatozoa during the hibernation season and to analyze whether TLRs play a role in sperm storage. The structure and ultrastructure of a spermatozoon during the hibernation stage were investigated using light‐ and transmission electron‐microscopy. RT‐PCR was used to analyze mRNA expression, while protein expression was determined via Western blot. TLR2/4 mRNA and proteins were detected in spermatozoa. Immunofluorescence staining was used to confirm TLR2/4 localization in the spermatozoon, and TLR2/4 were localized in the midpiece and the posterior segment of the head of the spermatozoon, which corresponded to the cytoplasmic droplets (CDs) of the turtle spermatozoon. As TLRs play critical roles in detecting and responding to invading pathogens, this study provided molecular evidence that TLR2/4 might contribute to sperm storage in the epididymides. Anat Rec, 299:1578–1584, 2016. © 2016 Wiley Periodicals, Inc.
Evaluation of Muscle Fiber Types in German Shepherd Dogs of Different Ages
Authors: de A. Braga Sérgio , G. F. Padilha Felipe , M. R. Ferreira Ana
Published: August 2016

The objective of this study was to determine and confirm the percentage of type I and type II muscle fibers that comprise the Gluteus Medius muscle in male and female canines of the German Shepherd breed, with standardized care, in different age groups, using the enzyme histochemical method. Muscle samples were collected from the Gluteus Medius muscles of forty clinically healthy dogs of the German Shepherd breed using the technique of percutaneous needle muscle biopsy. The samples were evaluated using histological and enzyme histochemical methods. The percentages of type I and II fibers and the ratio between the quantity of type I fibers/quantity of type II fibers were evaluated using the parameters of weight, age group, correlation between sex and age group, and between the sexes. It was found that there was no significant difference in relation to the types of fibers for the parameters of weight, age group, and age of the females. The correlation between the ages of the males suggested an increase in the percentage of type I fibers, a decrease in the percentage of type II fibers, or an increase in the ratio during the aging process. It was concluded that there was a decrease in the percentage of type II fibers with advancing age in male dogs, but without significant difference in the percentage of type I and type II fibers in relation to the weight. Anat Rec, 299:1540–1547, 2016. © 2016 Wiley Periodicals, Inc.
Effect of in vivo and in vitro exposure to electrostatic field on some hematological parameters in rats
Authors: Harutyunyan Hayk , Mkrtchyan Vahe , Sukiasyan Karine , Sahakyan Gohar , Poghosyan Gayane , Soghomonyan Ani , Cherniavsky Eugene , Bondarenko Ekaterina , Shkumatov Vladimir
Published: August 2016

The aim of this study was to investigate the effect of the external electrostatic field (ESF) on some hematological parameters in rats. Both in vivo and in vitro experiments were carried out. In in vivo investigations, rats were exposed to ESF (200 kV/m) during short (1 h) and long periods (6 days, 6 h daily). For in vitro study, the blood of intact rats was exposed to ESF for 1 h. Blood hematology was measured using validated ABX Micros ESV 60 Veterinary Hematology Analyzer. DNA damage in blood leucocytes was detected by means of comet assay. ESF effect on blood cell count was mainly manifested in white blood cells (WBC) and platelets. Damage of WBC was shown both in vitro and in vivo despite alterations in the count. This means the observed increase in WBC count in some cases might be a result of WBC compensatory mobilization from the bone marrow. Red blood cell (RBC) count and related parameters were slightly affected by ESF. Nevertheless, alterations in the shape and size of RBC were manifested. All ESF effects were extinguished in 14 days after the end of exposure. Bioelectromagnetics. 37:513–526, 2016. © 2016 Wiley Periodicals, Inc.
Analgesic effect of repetitive transcranial magnetic stimulation (rTMS) in patients with chronic low back pain
Authors: Ambriz‐Tututi Mónica , Alvarado‐Reynoso Beatriz , Drucker‐Colín René
Published: August 2016

The objective of the present study was to assess the benefits of 1‐week repetitive transcranial magnetic stimulation (rTMS) in patients with chronic low back pain (LBP). The visual analogue scale (VAS), Short Form McGill pain questionnaire (SF‐MPQ), and Short Form 36 Health Survey were used to evaluate the effect of this treatment. Eighty‐two patients diagnosed with LBP were divided randomly into three groups: rTMS‐treated group, sham group, and physical therapy‐treated group. We observed a significant reduction in VAS and SF‐MPQ scores in the rTMS‐treated group, but not in the sham group. Moreover, patients who received rTMS had a lower mean pain score than patients treated with physical therapy. Our study suggests that rTMS produces safe, significant, and long‐term relief in patients with LBP without evident side effects. This study shows for the first time that long‐term repeated sessions of rTMS decrease pain perception of LBP. Bioelectromagnetics. 37:527–535, 2016. © 2016 Wiley Periodicals, Inc.
Characterization of a Clostridium beijerinckii spo0A mutant and its application for butyl butyrate production
Authors: Seo Seung‐Oh , Wang Yi , Lu Ting , Jin Yong‐Su , Blaschek Hans P.
Published: August 2016

Spo0A is a master regulator that governs the metabolic shift of solventogenic Clostridium species such as Clostridium beijerinckii. Its disruption can thus potentially cause a significant alteration of cellular physiology as well as metabolic patterns. To investigate the specific effect of spo0A disruption in C. beijerinckii, a spo0A mutant of C. beijerinckii was characterized in this study. In a batch fermentation with pH control at 6.5, the spo0A mutant accumulated butyrate and butanol up to 8.96 g/L and 3.32 g/L, respectively from 60 g/L glucose. Noticing the unique phenotype of the spo0A mutant accumulating both butyrate and butanol at significant concentrations, we decided to use the spo0A mutant for the production of butyl butyrate that can be formed by the condensation of butyrate and butanol during the ABE fermentation in the presence of the enzyme lipase. Butyl butyrate is a value‐added chemical that has numerous uses in the food and fragrance industry. Moreover, butyl butyrate as a biofuel is compatible with Jet A‐1 aviation kerosene and used for biodiesel enrichment. In an initial trial of small‐scale extractive batch fermentation using hexadecane as the extractant with supplementation of lipase CalB, the spo0A mutant was subjected to acid crash due to the butyrate accumulation, and thus produced only 98 mg/L butyl butyrate. To alleviate the butyrate toxicity, the biphasic medium was supplemented with 10 g/L CaCO3 and 5 g/L butanol. The butyl butyrate production was then increased up to 2.73 g/L in the hexadecane layer. When continuous agitation was performed to enhance the esterification and extraction of butyl butyrate, 3.32 g/L butyl butyrate was obtained in the hexadecane layer. In this study, we successfully demonstrated the use of the C. beijerinckii spo0A mutant for the butyl butyrate production through the simultaneous ABE fermentation, condensation, and extraction. Biotechnol. Bioeng. 2017;114: 106–112. © 2016 Wiley Periodicals, Inc.
Continuous multistep synthesis of perillic acid from limonene by catalytic biofilms under segmented flow
Authors: Willrodt Christian , Halan Babu , Karthaus Lisa , Rehdorf Jessica , Julsing Mattijs K. , Buehler Katja , Schmid Andreas
Published: August 2016

The efficiency of biocatalytic reactions involving industrially interesting reactants is often constrained by toxification of the applied biocatalyst. Here, we evaluated the combination of biologically and technologically inspired strategies to overcome toxicity‐related issues during the multistep oxyfunctionalization of (R)‐(+)‐limonene to (R)‐(+)‐perillic acid. Pseudomonas putida GS1 catalyzing selective limonene oxidation via the p‐cymene degradation pathway and recombinant Pseudomonas taiwanensis VLB120 were evaluated for continuous perillic acid production. A tubular segmented‐flow biofilm reactor was used in order to relieve oxygen limitations and to enable membrane mediated substrate supply as well as efficient in situ product removal. Both P. putida GS1 and P. taiwanensis VLB120 developed a catalytic biofilm in this system. The productivity of wild‐type P. putida GS1 encoding the enzymes for limonene bioconversion was highly dependent on the carbon source and reached 34 g Ltube−1 day−1 when glycerol was supplied. More than 10‐fold lower productivities were reached irrespective of the applied carbon source when the recombinant P. taiwanensis VLB120 harboring p‐cymene monooxygenase and p‐cumic alcohol dehydrogenase was used as biocatalyst. The technical applicability for preparative perillic acid synthesis in the applied system was verified by purification of perillic acid from the outlet stream using an anion exchanger resin. This concept enabled the multistep production of perillic acid and which might be transferred to other reactions involving volatile reactants and toxic end‐products. Biotechnol. Bioeng. 2017;114: 281–290. © 2016 Wiley Periodicals, Inc.
Model‐supported phototrophic growth studies with Scenedesmus obtusiusculus in a flat‐plate photobioreactor
Authors: Koller Anja Pia , Löwe Hannes , Schmid Verena , Mundt Sabine , Weuster‐Botz Dirk
Published: August 2016

Light‐dependent growth of microalgae can vary remarkably depending on the cultivation system and microalgal strain. Cell size and the pigmentation of each strain, as well as reactor geometry have a great impact on absorption and scattering behavior within a photobioreactor. In this study, the light‐dependent, cell‐specific growth kinetics of a novel green algae isolate, Scenedesmus obtusiusculus, was studied in a LED‐illuminated flat‐plate photobioreactor on a lab‐scale (1.8 L, 0.09 m2). First, pH‐controlled batch processes were performed with S. obtusiusculus at different constant incident photon flux densities. The best performance was achieved by illuminating S. obtusiusculus with 1400 μmol photons m−2 s−1 at the surface of the flat‐plate photobioreactor, resulting in the highest biomass concentration (4.95 ± 0.16 gCDW L−1 within 3.5 d) and the highest specific growth rate (0.22 h−1). The experimental data were used to identify the kinetic parameters of different growth models considering light inhibition for S. obtusiusculus. Light attenuation within the flat‐plate photobioreactor was considered by varying light transfer models. Based on the identified kinetic growth model of S. obtusiusculus, an optimum growth rate of 0.22 h−1 was estimated at a mean integral photon flux density of 1072 μmol photons m−2 s−1 with the Beer–Lambert law and 1590 μmol photons m−2 s−1 with Schuster's light transfer model in the flat‐plate photobioreactor. LED illumination was, thus, increased to keep the identified optimum mean integral photon flux density constant in the batch process assuming Schuster's light transfer model. Compared to the same constant incident photon flux density (1590 μmol photons m−2 s−1), biomass concentration was up to 24% higher using the lighting profile until a dry cell mass concentration of 14.4 ± 1.4 gCDW L−1 was reached. Afterward, the biomass concentration remained constant, whereas cell growth continued in the batch process with constant incident photon flux density. Finally, biomass concentration was 15.5 ± 1.5 gCDW L−1 and, thus, 7% higher compared to the corresponding batch process with lighting profile. Biotechnol. Bioeng. 2017;114: 308–320. © 2016 Wiley Periodicals, Inc.
Die Zellwand der Pilze als Korsett
Authors: Kothe Erika , Freihorst Daniela
Published: August 2016

Pilze bilden ein eigenständiges Reich innerhalb der Eukarya. Ihre typische Wuchsform wird durch die Zellwand bestimmt, die damit Funktion und Form verbindet. Bei den Pilzen ist neben Hefestadien insbesondere das filamentöse Wachstum zur Bildung eines verzweigten, aus einzelnen Hyphen bestehenden Mycels charakteristisch. Dabei wird an der wachsenden Hyphenspitze durch Fusion von Vesikeln mit den Enzymen der Zellwandsynthese die Zellwand synthetisiert, die im Wesentlichen aus dem Polymer Chitin, bestehend aus N‐Acetylglucosamin, und β‐1,3‐Glucan besteht. Deacetyliertes Glucosamin, Chitosan genannt, kommt insbesondere bei einer Untergruppe der Pilze, den Zygomycten, regelmäßig vor. Zellwandproteine können über β‐1,6‐Glucan eingebunden oder aufgelagert werden wie die für Pilze typischen Hydrophobine. Zum Aufbau einer extrazellulären Matrix werden α‐1,3‐Glucane gebildet. Durch Aneinanderlagern können sogar Strukturen wie die makroskopischen Fruchtkörper gebildet werden.
Von der “comparirten Anatomie” zur Veterinärmedizin: Neues vom Biologen Goethe
Authors: Hoßfeld Uwe , Levit Georgy S. , Reinhold Petra
Published: August 2016

Im Jahre 2016 jährt sich ein für die veterinärmedizinische Ausbildung und Forschung in Jena und Thüringen wichtiges Ereignis: die Gründung einer Tierarzneischule vor 200 Jahren. Es war kein Geringerer als Geheimrat Johann W. von Goethe (1749–1832), der dabei eine führende Rolle spielte.
Simultaneous determination of ginsenosides and bufadienolides in rat plasma after the oral administration of Shexiang Baoxin Pill for pharmacokinetic study by liquid chromatography tandem mass spectrometry following solid‐phase extraction
Authors: Tao Jianfei , Mao Ling , Zhou Bailun , Liu Qun , Yang Aigang , Wei Guobing , Liu Runhui , Zhang Wei‐dong , Xu Wen , Ye Ji
Published: August 2016

A sensitive and reliable bioanalytical method was established for quantitati\ve and pharmacokinetic investigation of nine ginsenosides and seven bufadienolides in rat plasma after the oral administration of Shexiang Baoxin Pill by liquid chromatography–electrospray ionization tandem mass spectrometry, using tinidazole and digoxin as internal standards (ISTDs). All of the analytes and ISTDs obtained satisfactory recoveries by solid‐phase extraction using an Oasis HLB μElution Plate, which was eluted with methanol and ethyl acetate successively, and chromatographic separation was achieved on a Shim‐pack XR‐ODSIIcolumn (75 × 2.0 mm, 2.2 μm) with gradient elution using a mixture of acetonitrile–0.1% formic acid solution (v/v) as the mobile phase at a flow rate of 0.3 mL/min. Detection was carried out by a triple‐quadrupole tandem mass spectrometry with positive/negative ion switching multiple reaction monitoring mode. All analytes showed good linearity over a wide concentration range (r2 > 0.99). The lower limit of quantification was in the range 0.625–12.5 ng/mL for bufadienolides and 2–5.5 ng/mL for ginsenosides, and the mean recoveries of all analytes were in the range 78.29–99.35%. The intra‐ and inter‐day precisions (RSD) were in the range 0.08–12.38% with the accuracies between 86.09 and 99.40%. The validated method was then successfully applied to pharmacokinetic study of the above 16 compounds in rat plasma. Pharmacokinetic results indicated that the developed extraction and analytical method could be employed as a rapid, effective technique for pharmacokinetic study of multiple components, especially various polarity that are difficult to extract simultaneously.
Education on visualization of some complex physics problems in programing environment
Authors: Genç Hasan Hakan , Aydin Serkan
Published: August 2016

The realization of effective physics applications is thought as a privileged phenomenon due to the lack of transferring the basic laws of physics to produce products. In addition, the development of some applications depending on theory causes the discussion and questioning of scholars and competences which must be suitable for life. Assessment made with undergraduates and scholars shows that some difficulties are observed on embodiment of some physics problems in engineering and technical sciences. There are a lot of licensed softwares for analyzing the complex physical problems in technical fields. But these programs only help analyze the problems temporarily and they rarely help in long‐term conceptualization of solving the problem. For undergraduates, embodiment of physics problems involved with related discipline will help them conceptualize these subjects permanently. For this purpose, some physics problems involved with electronic engineering, which are hardly conceptualized by students, have been selected as a pilot. The effects of temperature and the other parameters on the silicon semiconductor for both the forward and reverse‐bias modes of operation curve, obtaining the hysteresis diagram for a control circuit and the visualization of hysteresis curve, the using of Monte Carlo statistically methods in numerical analysis of electromagnetic problems and the visualization of this method, are some selected subjects as a pilot. It is evaluated that besides classical teaching methods, approach will be discussed to help students analyze more complex physical problems if it is used as a methods in applied courses. © 2016 Wiley Periodicals, Inc. Comput Appl Eng Educ 24:876–886, 2016; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21757
Manage trademark troubles, mascot mayhem with legal strategies for protecting your school's brand
Authors: McCarthy Claudine
Published: August 2016

DALLAS — Unless you take the proper protective measures, your school's logo and mascot could be used without permission to profit others at the expense of damaging your school's brand, reputation, and image. In fact, it's a common occurrence for opportunistic individuals to hijack highly respected, well‐recognized logos and mascots that had been associated with a particular school for decades.
Thinking outside the box: Use of the pressure wire to assess intracranial large artery stenoses
Authors: Sanon Vani P. , Prasad Anand
Published: August 2016

Key points

A novel study investigating the utility of the 0.014″ diameter pressure wire to assess the hemodynamic significance of intermediate intracranial stenosis.

Technical aspects of pressure wire positioning across intracranial arteries are described.

Further research is required to clarify the assessment of pressure gradients in the cerebral circulation and to define the optimal threshold for intervention.
Management of vascular access after TAVR: Let's keep it simple
Authors: Safian Robert D. , Hanzel George
Published: August 2016

Key points

Bleeding and vascular complications are major causes of morbidity and mortality after transfemoral TAVR.

Compared with standard approaches to hemostasis, the catheter balloon occlusion technique CBOT) resulted in significant reduction in major bleeding and vascular complications (18.6% vs. 5.5%, P = 0.042).

Femoral crossover could not be achieved in 3.6%, and CBOT led to vessel dissection in 7.2%, major or life‐threatening bleeding in 5.5%, need for transfusion > 2 units in 10.9%, and minor bleeding or hematoma in 21.8% of patients.
Optimal anticoagulation prior to cath: Bivalirudin vs. Heparin the saga continues…
Authors: Belardi Jorge A. , Albertal Mariano
Published: August 2016

Key Points

During the pre‐procedural (medication) phase, the use of bivalirudin monotherapy is associated with the lowest rate of bleeding in patients with Non‐ST elevation myocardial infarction (Non‐STEMI) undergoing an early invasive strategy.

Monotherapy with either bivalirudin or unfractionated heparin (UFH) appear interchangeable in this setting.

The use of GPI upstream with either drug should be discouraged due to an increased risk of bleeding and net adverse events.

The use of low dose aspirin plus potent P2Y12 inhibitors followed by a transradial approach with implantation of drug‐eluting coronary stents with fluorinated polymers represents an strategy that may help limit perioperative ischemic and hemorrhagic complications in these individuals.
Airway obstruction caused by rapid enlargement of cervical lymphangioma in a five‐month‐old boy
Authors: Shimizu Junji , Taga Takashi , Kishimoto Takuma , Ohta Motoki , Tagawa Kouji , Kunitsu Tomoaki , Yamane Tetsunobu , Tsujita Yasuyuki , Kubota Yoshihiro , Eguchi Yutaka
Published: August 2016

Key Clinical Message

Cervical lymphangioma can cause airway obstruction secondary to enlargement following infection. Physicians should be aware that the airway obstruction can progress rapidly when patients with cervical lymphangioma have respiratory symptoms. Sclerotherapy for lymphangioma can cause both transient swelling and airway obstruction; thus, prophylactic and elective tracheostomy should be considered.
Mechanism and Origin of Selectivity in Platinum(II)‐Catalyzed Reactions of Acyclic γ,δ‐Ynones with Alkenes
Authors: Zhang Sujuan , Lv Pingli , Jia Chuanyi , Zhu Rongxiu , Lu Tongxiang , Wheeler Steven E.
Published: August 2016

The generation of platinum‐containing carbonyl ylides from acyclic γ,δ‐ynones and the cycloaddition of these ylides with electron‐rich alkenes have been explored computationally to explain the experimentally observed regio‐ and stereoselectivity. Three pathways for the reaction of ylides with methyl vinyl ether have been investigated. Two of these involve [3+2] cycloadditions, whereas the third involves a [4+2] cycloaddition. Results indicate that the operative reaction pathway depends on the substitution pattern of the acyclic γ,δ‐ynone. For an acyclic γ,δ‐ynone without a methyl substituent at the propargylic position, we predict that both [3+2] cycloaddition pathways are more favorable than the [4+2] cycloaddition pathway, which leads to two products. On the other hand, for an acyclic γ,δ‐ynone with a methyl substituent at the propargylic position, one of the [3+2] pathways is predicted to dominate, which exclusively affords an exo product. This feature arises from the hyperconjugative stabilization effect of the methyl group. Further analysis indicates that steric interactions between the chlorine atom of the catalyst and the methyl group of the vinyl ether lead to the observed exo selectivity. In all cases, the cycloaddition is the rate determining step, whereas for chiral PtCl2(bisphosphine)‐catalyzed reactions it is also stereodetermining, the high degree of enantioselectivity arises from differences in both noncovalent dispersion interactions and extent of partial bond formation in the key transition states for the [3+2] cycloaddition.
Ytterbium(III) Trifluoromethanesulfonate Catalyzed Ring‐Opening C(sp3)−N Bond Formation of Benzoxazoles with Propargylic Alcohols
Authors: Liu Wenfei , Sun Yongqing , Zhao Haiying , Li Baoguo , Chen Shufeng
Published: August 2016

A novel ytterbium(III) trifluoromethanesulfonate [Yb(OTf)3]‐catalyzed ring‐opening C(sp3)−N bond formation reaction of benzoxazole with propargylic alcohols was established. This reaction uses readily available starting materials and is operationally simple; it thus represents a practical method for the construction of highly functionalized substituted benzenes bearing aldehyde, propargylamine, and hydroxy groups with high atom economy.
Between Adamantane and Atrane: Intrabridgehead Interactions in the Cage‐Like Phosphane Related to a Novel Tris(homoadamantane) Ring System
Authors: Britvin Sergey N. , Rumyantsev Andrey M. , Zobnina Anastasia E. , Padkina Marina V.
Published: August 2016

Herein, we report unusual four‐center interactions in the novel cage‐like phosphane, 1,4,7‐triaza‐9‐phosphatricyclo[5.3.2.14,9]tridecane (CAP). This water‐soluble ligand, the first example of a tris(homoadamantane) ring system, can be considered a macrocyclic homologue of the well‐known PTA (1,3,5‐triaza‐7‐phosphaadamantane). However,31P NMR spectroscopic anomalies of CAP follow those typical for the bi‐/tricyclic atrane systems. Another atrane‐like feature of CAP is the ability of one nitrogen atom to undergoout–inpyramidal inversion. The latter is associated with a substantial decrease in the intracage N−N and P−N distances. Analysis of electron density distribution [molecular electrostatic potential (MESP) and atoms‐in‐molecules (AIM) approaches] suggests that the P and N atoms in the pyramidally inverted CAP derivatives are involved in interactions resulting in accumulation of electron density at the center of the phosphane cage. The latter can reliably explain the stereoelectronic and NMR anomalies of the new ligand. The semi‐flexible CAP cage populates the structural niche between the rigid adamantine skeleton of PTA and flexible atrane systems and can be regarded as an alternative to PTA in aqueous coordination chemistry.
Unprecedented Double aza‐Michael Addition within a Sapphyrin Core
Authors: Figueira Flávio , Marques Igor , Farinha Andreia S. F. , Tomé Augusto C. , Cavaleiro José A. S. , Silva Artur M. S. , Sessler Jonathan , Félix Vítor , Tomé João P. C.
Published: August 2016

A novel sapphyrin derivative was obtained from the reaction between a free‐base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza‐Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units. The present study provides a seemingly unprecedented example of an N,N′‐dinucleophile reacting with DMAD to form a heterocyclic compound in which the two N‐atoms are linked to the two sp3 carbon atoms derived from a substituted acetylene.
A Stable Extra‐Large‐Pore Zeolite with Intersecting 14‐ and 10‐Membered‐Ring Channels
Authors: Gao Zi‐Hao , Chen Fei‐Jian , Xu Lei , Sun Lin , Xu Yan , Du Hong‐Bin
Published: August 2016

The development of inorganic frameworks with extra‐large pores (larger than 12‐membered rings) has attracted considerable attention because of their potential applications in catalysis, the separation of large molecules, and so forth. We herein report the synthesis of the new extra‐large‐pore zeolite NUD‐2 by using the supramolecular self‐assembly of simple aromatic organic cations as structure‐directing agents (SDAs). NUD‐2 is a high‐silicon‐content germanosilicate with interconnecting 14×10‐membered‐ring channels. The SDAs in NUD‐2 can be removed by calcination in air at 550 °C to yield permanent pores with a BET surface area of 500 m2g−1. Both germanium and organic cations in NUD‐2 can also be removed by treatment with acid at lower temperature, thus not only affording recycling of germanium and SDAs, but also providing a highly stable siliceous zeolite. In addition, aluminum ions can be incorporated into the framework of NUD‐2. The NUD‐2 structure is yet another extra‐large‐pore zeolite synthesized by using the supramolecular self‐assembling templating approach, thus demonstrating that this approach is a general and applicable strategy for synthesis of new large‐ and extra‐large‐pore zeolites.
Iterative method for frequency domain identification of continuous processes with delay time
Authors: Jin Qibing , He En , Wang Qi , Jiang Beiyan
Published: August 2016

Delay time that affects the performances of many control synthesis techniques in controlled systems is common in most chemical industries. Estimating the delay time is also a difficult problem in identification fields. In this paper, aiming at continuous processes with delay time, an iterative least square identification method is proposed in the frequency domain. By introducing a truncated first‐order Taylor expansion, the delay time term is linearized. Linear regression equation for least squares (LS) is directly derived from the transfer function whose nonlinear term is replaced by a linear one. For reducing the linear approximation error and getting more accurate estimations of the model parameters, an iterative algorithm is developed based on the LS. Moreover, the proposed method can be easily extended to a closed‐loop system without increasing the order of the identified model. Simulations verify the effectiveness, fast convergence rates, and robustness of the proposed identification algorithm.
Effect of a Non‐Ionic Surfactant on Xylene Removal in a Scoria‐Compost‐Based Biofilter
Authors: Amin Mohammad Mehdi , Rahimi Amir , Bina Bijan , Mohammadi Moghadam Fazel , Nourmoradi Heshmatollah , Heidari Mohsen
Published: August 2016

The effect of a non‐ionic surfactant, Tween‐20, on xylene removal performance of a previously acclimated scoria‐compost‐based biofilter was evaluated. In the presence of the surfactant, the maximum elimination capacities (ECmax) of 71.0, 84.1, and 93.6 g m−3 h−1 were obtained for xylene inlet loading rates (ILRs) of 114.9, 124.1, and 197.1 g m−3 h−1 at empty bed residence times (EBRTs) of 40, 60, and 90 s, respectively. When the biofilter was fed the nutrient solution with Tween‐20, the average removal efficiency (REavg) was increased approximately 13 and 14% at EBRTs of 40 s (ILRavg of 43–47 g m−3 h−1) and 60 s (ILRavg of 61 g m−3 h−1), respectively. This indicates that the surfactant improved the performance of the biofilter at moderate ILRs. However, the removal of xylene was not significantly affected by the surfactant at high ILRs, around which ECmax was achieved. This means that the non‐ionic surfactant probably had a positive effect on the biofiltration of xylene when the diffusion through the biofilm, rather than biodegradation rates, appears to be the main process governing the performance of biofilter. Overall, this study showed that Tween‐20, in terms of xylene removal efficiency, may not have similar effects on the performance of biofilter at various loading conditions.
Detection of Microbiological Content in Water as Indicator of Its Ecological State − Mini‐Review
Authors: Besarab Natalya Vasilievna , Novik Galina Ivanovna
Published: August 2016

Intense anthropogenic pressure on the native media causing grave ecological problems such as deficiency of drinking water, shift of natural evolution of ecosystems due to species extinction, emphasizes the need of accurate analytical systems for continuous environmental monitoring. Microorganisms as simple sensitive living units conducting nutrient metabolic cycles in the environment are applicable for proper assessment of ambient media state. The paper will review modes of microbial contribution in indication and will list important and standard micro‐indicators of water pollution. The article will describe up‐to‐date direct methods of pollutant detection and indirect indicator‐recognition techniques. The peculiarities and requirements of water quality monitoring correlated with high dynamics and mobility of aqueous media will be discussed.
X‐rays effects on cytoskeleton mechanics of healthy and tumor cells
Authors: Panzetta Valeria , De Menna Marta , Musella Ida , Pugliese Mariagabriella , Quarto Maria , Netti Paolo A. , Fusco Sabato
Published: August 2016

Alterations in the cytoskeleton structure are frequently found in several diseases and particularly in cancer cells. It is also through the alterations of the cytoskeleton structure that cancer cells acquire most of their common features such as uncontrolled cell proliferation, cell death evasion, and the gaining of migratory and invasive characteristics. Although radiation therapies currently represent one of the most effective treatments for patients, the effects of X‐irradiation on the cytoskeleton architecture are still poorly understood. In this case we investigated the effects, over time of two different doses of X‐ray irradiation, on cell cytoskeletons of BALB/c3T3 and Sv40‐transformed BALB/c 3T3 cells (SVT2). Biophysical parameters – focal adhesion size, actin bundles organization, and cell mechanical properties – were measured before and after irradiations (1 and 2 Gy) at 24 and 72 h, comparing the cytoskeleton properties of normal and transformed cells. The differences, before and after X‐irradiation, were revealed in terms of cell morphology and deformability. Finally, such parameters were correlated to the alterations of cytoskeleton dynamics by evaluating cell adhesion at the level of focal adhesion and cytoskeleton mechanics. X‐irradiation modifies the structure and the activity of cell cytoskeleton in a dose‐dependent manner. For transformed cells, radiation sensitively increased cell adhesion, as indicated by paxillin‐rich focal adhesion, flat morphology, a well‐organized actin cytoskeleton, and intracellular mechanics. On the other hand, for normal fibroblasts IR had negligible effects on cytoskeletal and adhesive protein organization. © 2016 Wiley Periodicals, Inc.
Disparate clinical activity of PD‐1 blockade in melanoma subtypes: Know thy enemy!
Authors: Bhatia Shailender , Margolin Kim
Published: August 2016

The 2 articles by Shousatri et al and Algazi et al in this issue of Cancer report the efficacy of programmed cell death receptor 1 (PD‐1) pathway blockade in metastatic acral/mucosal melanoma and uveal melanoma, respectively. The results point to the disparate activity of PD‐1 and PD‐1 ligand pathway blockade in these subtypes of melanoma and highlight the need to understand differences in the underlying biology of immune evasion in these and other malignancies as well as the need to identify mechanisms of success and failure of PD‐1 blockade.

See also pages 3344‐53 and 3354‐62.
Sexuality after a cancer diagnosis: A population‐based study
Authors: Jackson Sarah E. , Wardle Jane , Steptoe Andrew , Fisher Abigail
Published: August 2016

BACKGROUND

This study explored differences in sexual activity, function, and concerns between cancer survivors and cancer‐free controls in a population‐based study.

METHODS

The data were from 2982 men and 3708 women who were 50 years old or older and were participating in the English Longitudinal Study of Ageing. Sexual well‐being was assessed with the Sexual Relationships and Activities Questionnaire, and cancer diagnoses were self‐reported.

RESULTS

There were no differences between cancer survivors and controls in levels of sexual activity (76.0% vs 78.5% for men and 58.2% vs 55.5% for women) or sexual function. Men and women with cancer diagnoses were more dissatisfied with their sex lives than controls (age‐adjusted percentages: 30.9% vs 19.8% for men [P = .023] and 18.2% vs 11.8% for women [P = .034]), and women with cancer were more concerned about levels of sexual desire (10.2% vs 7.1%; P = .006). Women diagnosed < 5 years ago were more likely to report difficulty with becoming aroused (55.4% vs 31.8%; P = .016) and achieving orgasm (60.6% vs 28.3%; P < .001) and were more concerned about sexual desire (14.8% vs 7.1%; P = .007) and orgasmic experience (17.6% vs 7.1%; P = .042) than controls, but there were no differences in men.

CONCLUSIONS

Self‐reports of sexual activity and functioning in older people with cancer are broadly comparable to age‐matched, cancer‐free controls. There is a need to identify the causes of sexual dissatisfaction among long‐term cancer survivors despite apparently normal levels of sexual activity and function for their age. The development of interventions addressing low sexual desire and problems with sexual functioning in women is also important and may be particularly relevant for cancer survivors after treatment. Cancer 2016;122:3883–3891. © 2016 American Cancer Society.
Effect of Food and Esomeprazole on the Pharmacokinetics of Alectinib, a Highly Selective ALK Inhibitor, in Healthy Subjects
Authors: Morcos Peter N. , Guerini Elena , Parrott Neil , Dall Georgina , Blotner Steven , Bogman Katrijn , Sturm Carolina , Balas Bogdana , Martin‐Facklam Meret , Phipps Alex
Published: August 2016

Alectinib, an anaplastic lymphoma kinase (ALK) inhibitor, is approved for treatment of patients with ALK+ non–small cell lung cancer who have progressed, on or are intolerant to, crizotinib. This study assessed the effect of a high‐fat meal and the proton pump inhibitor, esomeprazole, on the pharmacokinetics (PK) of alectinib. This was an open‐label, 2‐group study in healthy subjects. In group 1 (n = 18), subjects were randomly assigned to a 2‐treatment (A, fasted conditions; B, following a high‐fat meal), 2‐sequence (AB or BA) crossover assessment, separated by a 10‐day washout. In group 2 (n = 24), subjects were enrolled in a 2‐period, fixed‐sequence crossover assessment to evaluate the effect of esomeprazole. PK parameters were evaluated for alectinib, its major similarly active metabolite, M4, and the combined exposure of alectinib and M4. Administration of alectinib following a high‐fat meal substantially increased the combined exposure of alectinib and M4 to 331% (90%CI, 279%–393%) and 311% (90%CI, 273%–355%) for Cmax and AUC0–∞, respectively, versus fasted conditions. Coadministration of esomeprazole had no clinically relevant effect on the combined exposure of alectinib and M4. Alectinib should be administered under fed conditions to maximize its bioavailability, whereas no restrictions are required with antisecretory agents.
Tracing the Fingerprint of Chemical Bonds within the Electron Densities of Hydrocarbons: A Comparative Analysis of the Optimized and the Promolecule Densities
Authors: Keyvani Zahra Alimohammadi , Shahbazian Shant , Zahedi Mansour
Published: August 2016

The equivalence of the molecular graphs emerging from the comparative analysis of the optimized and the promolecule electron densities in two hundred and twenty five unsubstituted hydrocarbons was recently demonstrated [Keyvani et al.Chem. Eur. J.2016,22, 5003]. Thus, the molecular graph of an optimized molecular electron density is not shaped by the formation of the C−H and C−C bonds. In the present study, to trace the fingerprint of the C−H and C−C bonds in the electron densities of the same set of hydrocarbons, the amount of electron density and its Laplacian at the (3, −1) critical points associated with these bonds are derived from both optimized and promolecule densities, and compared in a newly proposed comparative analysis. The analysis not only conforms to the qualitative picture of the electron density build up between two atoms upon formation of a bond in between, but also quantifies the resulting accumulation of the electron density at the (3, −1) critical points. The comparative analysis also reveals a unified mode of density accumulation in the case of 2318 studied C−H bonds, but various modes of density accumulation are observed in the case of 1509 studied C−C bonds and they are classified into four groups. The four emerging groups do not always conform to the traditional classification based on the bond orders. Furthermore, four C−C bonds described as exotic bonds in previous studies, for example the inverted C−C bond in 1,1,1‐propellane, are naturally distinguished from the analysis.