bluuebunny/crossref_metadata_2025 huggingface dataset:
Between Localization and Delocalization: Ru(cod)2+ Units in the Zintl Clusters [Bi9{Ru(cod)}2]3− and [Tl2Bi6{Ru(cod)}]2−
Authors: Lichtenberger Niels , Spang Nils , Eichhöfer Andreas , Dehnen Stefanie
Published: August 2017

Reactions of [K(crypt‐222)]2(TlBi3)⋅0.5 en (1 b) with [Ru(cod)(H2CC(Me)CH2)2] (A) in 1,2‐diaminoethane (en) led to the formation of two compounds with new bismuth‐rich cluster anions, [K(crypt‐222)]3[Bi9{Ru(cod)}2]⋅1.5 en (2) and [K(crypt‐222)]2[Tl2Bi6{Ru(cod)}]⋅2 tol (3), alongside the salt of a binary nido cluster, [K(crypt‐222)]3(Tl4Bi5)⋅2 en (4). The anions in 2 and 3 are two further examples of rare heterometallic clusters containing Ru atoms. As one cod ligand is retained on each Ru atom in both clusters, the anions may be viewed as intermediates on the way towards larger, ligand‐free intermetalloid clusters. Quantum‐chemical studies provided insight into the bonding situation in these clusters. According to these studies, the anion of 2 features both electron‐precise and electron‐deficient parts. Electrospray ionization mass spectrometry analysis indicated that the clusters undergo stepwise fragmentation.
The effect of aluminum alkyls and BHT‐H on reaction kinetics of silica supported metallocenes and polymer properties in slurry phase ethylene polymerization
Authors: Bashir Muhammad Ahsan , Monteil Vincent , Boisson Christophe , McKenna Timothy F. L.
Published: August 2017

In slurry and gas phase catalytic ethylene polymerization processes, aluminum alkyl (AlR3) compounds are usually present inside the reactor and their role either as co‐catalyst or scavenger is of considerable importance. Silica supported metallocene/methyl aluminoxane (MAO) catalysts show specific interactions with AlR3 compounds. Therefore, this study shows an attempt to analyze and compare the effect of concentration as well as type of commonly used AlR3 on slurry phase ethylene homopolymerization kinetics of silica supported (n‐BuCp)2ZrCl2/MAO catalyst. The obtained results indicate that the lower the concentration of smaller AlR3 compounds, the higher the instantaneous catalytic activity. Concerning the polymer particle size distributions, a rise in fines generation has been observed with increasing AlR3 content inside the reactor. Finally, it has been shown that the addition of 2,6‐di‐tert‐butyl‐4‐methylphenol (a substituted phenol) into the reactor containing AlR3 reduces the influence of AlR3 compounds on the reaction kinetics of silica supported metallocene/MAO catalysts. Polyethylene properties remain similar in all the studied scenarios. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45670.
Aromatic Regions Govern the Recognition of NADPH Oxidase Inhibitors as Diapocynin and its Analogues
Authors: Macías Pérez Martha E. , Hernández Rodríguez Maricarmen , Cabrera Pérez Laura C. , Fragoso‐Vázquez M. Jonathan , Correa‐Basurto José , Padilla‐Martínez Itzia I. , Méndez Luna David , Mera Jiménez Elvia , Flores Sandoval César , Tamay Cach Feliciano , Rosales‐Hernández Martha C.
Published: August 2017

Oxidative stress is related to the pathogenesis and progress of several human diseases. NADPH oxidase (NOX), and mainly the NOX2 isoform, produces superoxide anions (O2•−). To date, it is known that NOX2 can be inhibited by preventing the assembly of its subunits, p47phox and p22phox. In this work, we analyzed the binding to NOX2 of the apocynin dimer, diapocynin (C1), a known NOX2 inhibitor, and of 18 designed compounds (C2–C19) which have chemical relationships to C1, by in silico methods employing a p47phox structure from the Protein Data Bank (PDB code: 1WLP). C1 and six of the designed compounds were recognized in the region where p22phox binds to p47phox and makes π–π interactions principally with W193, W263, and Y279, which form an aromatic‐rich region. C8 was chosen as the best compound according to the in silico studies and was synthesized and evaluated in vitro. C8 was able to prevent the production of reactive oxygen species (ROS) similar to C1. In conclusion, targeting the aromatic region of p47phox through π‐interactions is important for inhibiting NOX activity.
A Facile Route to Ortho‐Hydroxyanilnes through an IrIII‐Catalyzed Direct C−H Amidation of 2‐Phenoxypyridines
Authors: Wang Lianhui , Yang Zi , Yang Mengqi , Tian Miaodou , Kuai Changsheng , Cui Xiuling
Published: August 2017

A highly efficient and regioselective IrIII‐catalyzed C−H amidation of 2‐phenoxypyridines has been developed by using sulfonyl azides as an amino source. The amidated products were provided in good‐to‐excellent yields with broad functional‐group tolerance. Furthermore, the 2‐pyridyl moiety in the amidated products could be readily removed, thus offering an efficient route to synthetically useful ortho‐hydroxyanilnes, which are important building blocks in organic synthesis.
CRISPRi repression of nonhomologous end‐joining for enhanced genome engineering via homologous recombination in Yarrowia lipolytica
Authors: Schwartz Cory , Frogue Keith , Ramesh Adithya , Misa Joshua , Wheeldon Ian
Published: August 2017

In many organisms of biotechnological importance precise genome editing is limited by inherently low homologous recombination (HR) efficiencies. A number of strategies exist to increase the effectiveness of this native DNA repair pathway; however, most strategies rely on permanently disabling competing repair pathways, thus reducing an organism's capacity to repair naturally occurring double strand breaks. Here, we describe a CRISPR interference (CRISPRi) system for gene repression in the oleochemical‐producing yeast Yarrowia lipolytica. By using a multiplexed sgRNA targeting strategy, we demonstrate efficient repression of eight out of nine targeted genes to enhance HR. Strains with nonhomologous end‐joining repressed were shown to have increased rates of HR when transformed with a linear DNA fragment with homology to a genomic locus. With multiplexed targeting of KU70 and KU80, and enhanced repression with Mxi1 fused to deactivated Cas9 (dCas9), rates of HR as high as 90% were achieved. The developed CRISPRi system enables enhanced HR in Y. lipolytica without permanent genetic knockouts and promises to be a potent tool for other metabolic engineering, synthetic biology, and functional genomics studies.
Reversible Loading of Nanoscale Elements on a Multicomponent Supramolecular Polymer System by Using DNA Strand Displacement
Authors: Noteborn Willem E. M. , Saez Talens Victorio , Kieltyka Roxanne E.
Published: August 2017

Nucleic acids are excellent building blocks to enable switchable character in supramolecular polymer materials because of their inherent dynamic character and potential for orthogonal self‐assembly. Herein, DNA‐grafted squaramide bola‐amphiphiles are used in a multicomponent supramolecular polymer system and it is shown that they can be addressed by DNAlabeled gold nanoparticles (5 and 15 nm) through sequence complementarity. These nanoparticles can be selectively erased or rewritten on‐demand by means of DNA‐strand displacement.
Construction of (Ni, Cu) Se2//Reduced Graphene Oxide for High Energy Density Asymmetric Supercapacitor
Authors: Chen Bo , Tian Yifan , Yang Zhaoxi , Ruan Yunjun , Jiang Jianjun , Wang Chundong
Published: August 2017

Selenide, particularly transition‐metal selenide, is gaining popularity for use as electrode materials in electrochemical capacitors, because they are low cost, highly conductive, earth abundant, and environmentally benign. Here, we fabricated (Ni, Cu) Se2 nanowires on nickel foam (NF) with a facile one‐pot hydrothermal method. Upon rational design and careful growth control, regular (Ni, Cu) Se2 nanowires of several micrometers in length were grown, having an areal specific capacitance of 5.92 F cm−2 at a current density of 2 mA cm−2. Afterwards, an asymmetric supercapacitor was assembled by selecting the (Ni, Cu) Se2 nanowire/NF as the positive electrode, and reduced graphene oxide (RGO) as the negative electrode, delivering an ultrahigh energy density of 44.46 Wh kg−1 at a power density of 797.9 W kg−1, and when tested at an ultrahigh power density of 9796.7 W kg−1, an energy density of 6.53 Wh kg−1 can be still maintained, evidencing its potential applications. Besides its high energy density features, it is impressive to notice that the energy density still maintains 97.56 % even after 4000‐cycle fierce cycling at an ultrahigh current density of 50 mA cm−2. To the best of our knowledge, it is the first‐ever reported (Ni, Cu) Se2‐based supercapacitor/asymmetric supercapacitor. This work may arouse new interest for designing and growing transition‐metal selenide and/or metal selenide for large‐scale, practical supercapacitor applications.
Dual‐Nuclide Radiopharmaceuticals for Positron Emission Tomography Based Dosimetry in Radiotherapy
Authors: Wurzer Alexander , Seidl Christof , Morgenstern Alfred , Bruchertseifer Frank , Schwaiger Markus , Wester Hans‐Jürgen , Notni Johannes
Published: August 2017

Improvement of the accuracy of dosimetry in radionuclide therapy has the potential to increase patient safety and therapeutic outcomes. Although positron emission tomography (PET) is ideally suited for acquisition of dosimetric data because PET is inherently quantitative and offers high sensitivity and spatial resolution, it is not directly applicable for this purpose because common therapeutic radionuclides lack the necessary positron emission. This work reports on the synthesis of dual‐nuclide labeled radiopharmaceuticals with therapeutic and PET functionality, which are based on common and widely available metal radionuclides. Dual‐chelator conjugates, featuring interlinked cyclen‐ and triazacyclononane‐based polyphosphinates DOTPI and TRAP, allow for strictly regioselective complexation of therapeutic (e.g., 177Lu, 90Y, or 213Bi) and PET (e.g., 68Ga) radiometals in the same molecular framework by exploiting the orthogonal metal ion selectivity of these chelators (DOTPI: large cations, such as lanthanide(III) ions; TRAP: small trivalent ions, such as GaIII). Such DOTPI–TRAP conjugates were decorated with 3 Gly‐urea‐Lys (KuE) motifs for targeting prostate‐specific membrane antigen (PSMA), employing Cu‐catalyzed (CuAAC) as well as strain‐promoted (SPAAC) click chemistry. These were labeled with 177Lu or 213Bi and 68Ga and used for in vivo imaging of LNCaP (human prostate carcinoma) tumor xenografts in SCID mice by PET, thus proving practical applicability of the concept.
Benign Synthesis of Black Microspheres of Anatase TiO2 with Paramagnetic Oxygen Vacancies through NH3 Treatment
Authors: Maqbool Qysar , Srivastava Aasheesh
Published: August 2017

Coloured TiO2 is coveted for its ability to extract energy from the visible region of electromagnetic spectrum. Here a facile synthesis of black anatase titania microspheres (B‐TiO2) through a two‐step process is reported. In the first step, amorphous white TiO2 microspheres (W‐TiO2) are obtained by hydrolysing titanium tetraisopropoxide by ammonia vapours in ethanol. In the second step, the W‐TiO2 is thermally annealed at 500 °C to obtain B‐TiO2. The diffuse reflectance analysis showed that B‐TiO2 absorbs across visible spectrum with absorption extending well into NIR region. Raman scattering together with EPR analysis showed compelling evidence of the existence of oxygen deficiency within the crystal in B‐TiO2 that induces black colouration in the sample. The defects present in the black anatase sample were confirmed to be single‐electron‐trapped (or paramagnetic) oxygen vacancies (Vo⋅) by XPS and EPR studies. The magnetic susceptibility studies showed existence of antiferromagnetic interactions between these unpaired electron spins.
From a Diphosphanegermylene to Nickel, Palladium, and Platinum Complexes Containing Germyl PGeP Pincer Ligands
Authors: Álvarez‐Rodríguez Lucía , Brugos Javier , Cabeza Javier A. , García‐Álvarez Pablo , Pérez‐Carreño Enrique
Published: August 2017

The PGeP pincer‐type germylene Ge(NCH2PtBu2)C6H4 (1) has been used to prepare a family of group 10 metal complexes, namely, [MCl{κ3P,Ge,P‐GeCl(NCH2PtBu2)2C6H4}] (M=Ni (2Ni), Pd (2Pd), Pt (2Pt)), featuring a chloridogermyl PGeP pincer ligand and a Cl−Ge−M−Cl bond sequence. Their reactivity is not initially centered on the metal atom but on their Ge atom. Complexes 2Ni and 2Pd easily led to the hydrolyzed products [Ni2Cl2{μ‐(κ3P,Ge,P‐Ge(NCH2PtBu2)2C6H4)2O}], which features a Cl−Ni−Ge−O−Ge−Ni−Cl bond sequence, and [PdCl{κ3P,Ge,P‐Ge(OH)(NCH2PtBu2)2C6H4}], which contains a hydroxidogermyl PGeP pincer ligand (2Pt is reluctant to undergo hydrolysis). Simple chloride exchange reactions led to the methoxidogermyl, methylgermyl, and phenylgermyl derivatives [MCl{κ3P,Ge,P‐GeR(NCH2PtBu2)2C6H4}] (M=Pd, Pt; R=OMe, Me, Ph). Whereas the palladium complexes [PdCl{κ3P,Ge,P‐GeR(NCH2PtBu2)2C6H4}] (R=Me, Ph) reacted with more MeLi or PhLi to give palladium black and GeR2(NCH2PtBu2)2C6H4 (R=Me, Ph), similar reactions with the analogous platinum complexes afforded the transmetalation derivatives [PtR{κ3P,Ge,P‐GeR(NCH2PtBu2)2C6H4}] (R=Me, Ph). The short length of the CH2PtBu2 arms of the PGeP pincer ligands forces the metal atoms of all these complexes to be in a very distorted square‐planar ligand environment. The reactivity results have been rationalized with theoretical calculations.
Design, Synthesis, and Characterization of Brequinar Conjugates as Probes to Study DHODH Inhibition
Authors: Madak Joseph T. , Cuthbertson Christine R. , Chen Wenmin , Showalter Hollis D. , Neamati Nouri
Published: August 2017

Brequinar, a potent dihydroorotate dehydrogenase (DHODH) inhibitor, has been evaluated in multiple clinical trials as a potential treatment for cancer. To further understand brequinar‐based DHODH inhibition and DHODH′s therapeutic relevance in cancer, we have developed novel brequinar‐based probes. We disclose a 16‐step convergent synthesis of the first brequinar‐PROTAC and a four‐step approach towards the first mitochondrial‐directed brequinar probe. A PROTAC and mitochondria‐directed probe of brequinar both possess cytotoxicity that is superior to brequinar in a colony formation assay.
Unexpected Rotamerism at the Origin of a Chessboard Supramolecular Assembly of Ruthenium Phthalocyanine
Authors: Mattioli Giuseppe , Larciprete Rosanna , Alippi Paola , Bonapasta Aldo Amore , Filippone Francesco , Lacovig Paolo , Lizzit Silvano , Paoletti Anna Maria , Pennesi Giovanna , Ronci Fabio , Zanotti Gloria , Colonna Stefano
Published: August 2017

We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc)2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru−Ru bond, (RuPc)2 can be found in two stable rotameric forms separated by a low‐energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard‐like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π‐stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc)2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices.
Locally Excited State–Charge Transfer State Coupled Dyes as Optically Responsive Neuron Firing Probes
Authors: Sirbu Dumitru , Butcher John B. , Waddell Paul G. , Andras Peter , Benniston Andrew C.
Published: August 2017

A selection of NIR‐optically responsive neuron probes was produced comprising of a donor julolidyl group connected to a BODIPY core and several different styryl and vinylpyridinyl derived acceptor moieties. The strength of the donor–acceptor interaction was systematically modulated by altering the electron withdrawing nature of the aryl unit. The fluorescence quantum yield was observed to decrease as the electron withdrawing effect of the aryl subunit increased in line with changes of the Hammett parameter. The effectiveness of these fluorophores as optically responsive dyes for neuronal imaging was assessed by measuring the toxicity and signal‐to‐noise ratio (SNR) of each dye. A great improvement of SNR was obtained when compared to the first‐generation BODIPY‐based voltage sensitive dyes with concomitant toxicity decrease. The mechanism for the optical response is disparate from conventional cyanine‐based dyes, opening up a new way to produce effective voltage sensitive dyes that respond well into the NIR region.
Proof of Concept Studies Directed Towards Designed Molecular Wires: Property‐Driven Synthesis of Air and Moisture‐Stable Polystannanes
Authors: Pau Jeffrey , Lough Alan J. , Wylie R. Stephen , Gossage Robert A. , Foucher Daniel A.
Published: August 2017

Polystannanes with azobenzene moieties designed to protect the Sn–Sn backbone from light‐ and moisture‐induced degradation are described. The azo‐stannyl precursor 3 (70 %) is converted in good yields (88–91 %) to the mono‐ (4), and dichlorostannanes (5), by sequential chlorination, followed by further reduction of 5 to the dihydride (6) using NaBH4 (78 %). All stannanes were characterised by NMR (1H, 13C, 119Sn) spectroscopy and HRMS; in addition, 3, 4 and 5 were structurally elucidated using X‐ray diffraction analysis. Metal‐free dehydrocoupling of 6 at RT leads exclusively to homopolymer (7‐i) displaying an initial solution 119Sn NMR signal (δ=−196 ppm) that migrates to −235 ppm after 10 days (7‐f). In contrast, metal‐catalyzed dehydrocoupling of 6 in toluene at RT leads directly 7‐f. Random co‐polymers formed from 6 and (nBu)2SnH2 at 4:1 (8 a) and 1:1 (8 b) ratios were compared to the alternating polystannane (9) prepared by the reaction of 6 with (nBu)2Sn(NEt2)2. DFT calculations of 3–6 indicate that hypercoordination at Sn is influenced by substituents and by solvation. Homopolymer 7 was found to have unprecedented moisture and light stability in the solid state for >6 months.
Switching of Reaction Pathway from C−C Rollover to C−N Ring‐Extension Annulation
Authors: Thenarukandiyil Ranjeesh , Dutta Champak , Choudhury Joyanta
Published: August 2017

This work discloses that a simple change in the anion of a copper(II) reagent along with the reaction solvent can dramatically alter the course of a Cp*RhIII‐catalyzed C−H activation–annulation reaction leading to completely switchable chemoselective products. The nature of the anion in terms of its coordinating ability and basicity, and also the polarity of the solvent have been found to be the crucial factors in the observed divergence.
Asymmetric Aminalization via Cation‐Binding Catalysis
Authors: Park Sang Yeon , Liu Yidong , Oh Joong Suk , Kweon Yoo Kyung , Jeong Yong Bok , Duan Mengying , Tan Yu , Lee Ji‐Woong , Yan Hailong , Song Choong Eui
Published: August 2017

Asymmetric cation‐binding catalysis, in principle, can generate “chiral” anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope of the reaction. Particularly, a formation of configurationally labile aminal centers with alkyl substituents has been a formidable challenge due to the enamine/imine equilibrium of electrophilic substrates. Herein, we report enantioselective nucleophilic addition reactions of potassium phthalimides to Boc‐protected alkyl‐ and aryl‐substituted α‐amido sulfones. In situ generated imines smoothly reacted with the nitrogen nucleophiles to corresponding aminals with good to excellent enantioselectivitiy under mild reaction conditions. In addition, transformation of aminal products gave biologically relevant pyrrolidinone‐fused hexahydropyrimidine scaffold with excellent stereoselectivity and good yield.
Online incipient fault diagnosis based on Kullback‐Leibler divergence and recursive principle component analysis
Authors: Chai Yi , Tao Songbing , Mao Wanbiao , Zhang Ke , Zhu Zhiqin
Published: August 2017

Fault detection and isolation (FDI) methods based on the principal component analysis (PCA) model have achieved a large number of theoretical studies and applications, especially for complex and highly dimensional processes. However, the Hotelling's T2, that is the most common used statistical distance, can fail in detecting small shifts such as a sensor incipient fault with low fault‐to‐noise ratio (FNR). Although an incipient fault develops slowly, it cannot be ignored and is necessary to be detected early enough to avoid more serious consequences. In this study, a realistic online diagnosis method for incipient faults with low FNR is presented. Based on probability distribution measure, the Kullback‐Leibler divergence (KLD) is utilized to compare the probability density of each of the latent scores to a reference one. Under the hypothesis of Gaussian distribution, dynamic changes of KLDs are computed via the mean and variance of score vectors, which can be updated online utilizing the recursive principal component analysis (RPCA). From simulations, it is shown that the proposed approach can detect, isolate, and estimate the sensor incipient fault of the multivariate AR system successfully.
Application of a screening method for fentanyl and its analogues using UHPLC‐QTOF‐MS with data‐independent acquisition (DIA) in MSE mode and retrospective analysis of authentic forensic blood samples
Authors: Noble Carolina , Weihe Dalsgaard Petur , Stybe Johansen Sys , Linnet Kristian
Published: August 2017

The steady appearance of new fentanyl analogues and the associated overdose deaths require the development of sensitive screening approaches to detect these compounds in biological samples and seizures. We developed a targeted screening method to detect 50 4‐anilidopiperidine‐related fentanyl analogues in whole blood using ultra‐high performance liquid chromatography quadrupole time‐of‐flight mass spectrometry in data‐independent acquisition mode. Sample preparation was performed using protein precipitation on a fully automated robotic setup. Thirteen analogues were selected to validate the method. A small matrix ion enhancement effect (110–123%) was observed for all of the compounds; the recovery ranged from 67% to 81% and the process efficiency from 81% to 98%. Limit of detection was within 0.0005–0.001 mg/kg and limit of identification ranged from 0.001 to 0.005 mg/kg. In the retrospective analysis of 2339 forensic blood samples, the major finding was fentanyl (n = 56), followed by alfentanil (n = 5) and remifentanil (n = 1). Identification of 34 fentanyl analogues was based on the predicted product ions resulting from common fentanyl‐specific collision‐induced cleavages, particularly on the product ion result of the fragmentation on the C‐N bond between the phenylamide moiety and the piperidine ring. The proposed hypothesis was supported by the targeted analysis of 16 fentanyl analogues using this method and available published mass spectral data sources for fentanyl analogues. A targeted screening method for 50 fentanyl analogues was successfully validated and implemented to analyse authentic blood samples, where identifying targeted fentanyl analogues was tentatively achieved without using reference standards.
Selective Recovery of Silver(I) Ions from E‐Waste using Cubically Multithiolated Cage Mesoporous Monoliths
Authors: Elshehy Emad A. , Shenashen Mohamed A. , Abd El‐Magied Mahmoud O. , Tolan Dina A. , El‐Nahas Ahmed M. , Halada Kohmei , Atia Asem A. , El‐Safty Sherif A.
Published: August 2017

We report the selective engineering of hybrid organic mesoporous silica monolith adsorbents for the recovery of silver (Ag) ions from e‐waste samples. The AgI multithiolated adsorbent scales were synthesized through dense and continuous surface modifications of hierarchically ordered mesoporous (HOM) monoliths by active organic moieties. Captured subsets were created on the monolithic surfaces and in the orderly pore cavities for suitable AgI trapping. In addition, HOM monolithic carriers, with unique surface dominants, micrometer‐sized particles, high surface‐area/pore‐volume ratios, and uniform groove‐like cage cavities, form neat rooms for target ions. The decoration and depression of the extraordinary micrometer‐sized surface monoliths and the orderly neat grooves enable the adsorption of large quantities and well‐dispersed coverage of the multithiolated layers. These layers include sulfur‐ and nitrogen‐active sites that selectively improve AgI adsorption/trapping/capture among competitive matrices. Results indicate that the adsorption of AgI is strong at pH 6.5 and it appears to follow the Langmuir adsorption model, with a maximum capacity of 179.23 mg g–1. The hierarchical multithiolated adsorbent scales exhibit selectivity for Ag ions in the presence of coexisting cations. The retention of the organic structure and orientation along the HOM monoliths enables multiple‐use recovery, collection, and management of AgI, without altering their functionality and capacity. The results suggest that the hierarchical adsorbent scales are suitable for AgI recovery from aquatic samples.
Effects of Adsorption on Polycyclic Aromatic Hydrocarbon, Lipid Characteristic, Oxidative Stability, and Free Radical Scavenging Capacity of Sesame Oil
Authors: Shi Long‐Kai , Zheng Li , Jin Qing‐Zhe , Wang Xing‐Guo
Published: August 2017

Treatment with three adsorbents led to reductions of PAHs in sesame oils, and activated carbons are more effective for removal of PAHs than activated clay under the experimental conditions. Fatty acid, triacylglycerol, and γ‐tocopherol profiles of sesame oils are not significantly influenced by addition of any adsorbents. However, significant differences (P < 0.05) are observed in the contents of other minor components, oxidation stability and free radical scavenging capacity between the crude and treated sesame oils. Polyphenol and phytosterol are good predictors of oxidative stability and antioxidant capacity of sesame oils, due to significant correlations are observed. Although adsorption process may bring disadvantage to sesame oils such as reductions of beneficial constituents related to storage stability, free radical scavenging capacity and other physiological functions, however, to eliminate the contamination of PAHs, treatment with activated carbon during sesame oil purification is highly recommended in order to reduce the risk of consumption and to assure the consumer health. Moreover, these results provide a useful guidance for sesame oil plant to improve the quality of the final oil product. Practical Applications: Results of this study can be applied to sesame oil plants and are transferable to other flavor edible oils for which lower the risk of consumption and bring economic and social advantages to manufacturers to guarantee the oil quality and consumer health.

In this work, the contents of polycyclic aromatic hydrocarbon, lipid characteristic, oxidative stability, and free radical scavenging capacity of sesame oil during adsorption process are investigated and compared. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) showed apparent distinctions between the crude and treated sesame oils, thus illustrated that adsorption is a double‐edged sword to sesame oils.
Perinatal lead (Pb) exposure results in sex and tissue‐dependent adult DNA methylation alterations in murine IAP transposons
Authors: Montrose L. , Faulk C. , Francis J. , Dolinoy D.C.
Published: August 2017

Epidemiological and animal data suggest that adult chronic disease is influenced by early‐life exposure‐induced changes to the epigenome. Previously, we observed that perinatal lead (Pb) exposure results in persistent murine metabolic‐ and activity‐related effects. Using phylogenetic and DNA methylation analysis, we have also identified novel intracisternal A particle (IAP) retrotransposons exhibiting regions of variable methylation as candidate loci for environmental effects on the epigenome. Here, we now evaluate brain and kidney DNA methylation profiles of four representative IAPs in adult mice exposed to human physiologically relevant levels of Pb two weeks prior to mating through lactation. When IAPs across the genome were evaluated globally, average (sd) methylation levels were 92.84% (3.74) differing by tissue (P < 0.001), but not sex or dose. By contrast, the four individual IAPs displayed tissue‐specific Pb and sex effects. Medium Pb‐exposed mice had 3.86% less brain methylation at IAP 110 (P < 0.01), while high Pb‐exposed mice had 2.83% less brain methylation at IAP 236 (P = 0.01) and 1.77% less at IAP 506 (P = 0.05). Individual IAP DNA methylation differed by sex for IAP 110 in the brain and kidney, IAP 236 in the kidney, and IAP 1259 in the kidney. Using Tomtom, we identified three binding motifs that matched to each of our novel IAPs impacted by Pb, one of which (HMGA2) has been linked to metabolic‐related conditions in both mice and humans. Thus, these recently identified IAPs display tissue‐specific environmental lability as well as sex‐specific differences supporting an epigenetic link between early exposure to Pb and later‐in‐life health outcomes. Environ. Mol. Mutagen. 58:540–550, 2017. © 2017 Wiley Periodicals, Inc.
Genomic damage induced by 1‐MHz ultrasound in vitro
Authors: Udroiu Ion , Marinaccio Jessica , Bedini Angelico , Giliberti Claudia , Palomba Raffaele , Sgura Antonella
Published: August 2017

Genotoxic effects of therapeutic ultrasound are poorly documented, when compared with the wide use of this physical agent. The aim of this work was to investigate the clastogenic and aneugenic potential of 1 MHz ultrasound, employing intensities (200 and 300 mW/cm2) above the cavitational threshold, but in the range of those normally used in therapeutics. Both normal fibroblasts (AG01522) and tumoral cells (MCF‐7) were sonicated. While no effects on viability were noted, significant increases of CREST‐negative micronuclei (indicative of clastogenesis) and CREST‐positive micronuclei (indicative of aneuploidy) were detected. Clastogenesis was confirmed by increases of γ‐H2AX foci, while increases of spindle anomalies confirmed the induction of aneuploidy. Our results confirm previous works that showed ultrasound‐induced DNA breakage. Moreover, our experiments show that the known effect of ultrasound‐induced damage to microtubules is also able to damage the mitotic spindle and induce aneuploidy. On the overall, this work highlights the importance to further investigate the potential risks related to therapeutics US. Environ. Mol. Mutagen. 59:60–68, 2018. © 2017 Wiley Periodicals, Inc.
Personalized safety measures reduce the adverse event rate of long‐term video EEG
Authors: Dobesberger Judith , Höfler Julia , Leitinger Markus , Kuchukhidze Giorgi , Zimmermann Georg , Thomschewski Aljoscha , Unterberger Iris , Walser Gerald , Kalss Gudrun , Rohracher Alexandra , Neuray Caroline , Kobulashvili Teia , Höller Yvonne , Trinka Eugen
Published: August 2017

Objective

Safety in epilepsy monitoring units (EMUs) has become an increasing concern because adverse events occur in up to 10% of patients undergoing long‐term video EEG in EMUs. The aim of this study was to assess the effectiveness of a specific safety protocol in an EMU.

Methods

We retrospectively assessed the adverse event rates in a group without (group 1, 84‐month period, Innsbruck, Austria) and a group with (group 2, 33‐month period, Salzburg, Austria) personalized safety measures utilizing a standardized protocol for long‐term epilepsy monitoring in high‐risk patients. Differences in adverse event rates during and after long‐term video EEG between the two groups were calculated and compared.

Results

In group 1, 44/507 (9%, 95% confidence interval [CI] 6.5–11.5%) patients experienced 53 adverse events: 20/507 (4%, 95% CI 2.6–6.0%) patients had psychiatric events, 15/507 (3%, 95% CI 1.8–4.8%) patients sustained a total of 19 injuries during seizures, and 10/507 (2%, 95% CI 1.1–3.6%) patients had 13 episodes of status epilepticus; one adverse event was treatment‐related (valproic acid–induced encephalopathy; 1/507, 0.2%, 95% CI 0.0–1.1%). By using the new safety protocol in group 2, the adverse event rate was only 5% (95% CI 3.4–7.6%; 30 adverse events in 26/491; 45% reduction; p = 0.036), in contrast. These events included 13 psychiatric complications in 13/491 (2%, 95% CI 1.6–4.5%, p = 0.252) patients, 12 seizure‐related injuries in 9/491 (2%, 95% CI 1.0–3.4%, p = 0.250) patients, and 5 episodes of status epilepticus in 4/491 (1%, 95% CI 0.3–2.1%, p = 0.120) patients.

Significance

Implementation of personalized safety measures in high‐risk patients resulted in a clinically relevant reduction of adverse events in the EMU. Safety protocols are a valid tool to reduce the occurrence of adverse events in EMUs.
The importance of maintenance conditions of Daphnia magna Straus as a test organism for ecotoxicological analysis
Authors: Olkova Anna S. , Kantor Grigorii Y. , Kutyavina Tatyana I. , Ashikhmina Tamara Y.
Published: August 2017

Insufficient attention to the standardization of conditions for test organisms can lead to a distortion of bioassay results by changing the characteristics of the culture. The present study deals with the influence of abiotic factors (temperature of cultivated water, its chemical composition, season of the year) and biotic factors (seeding density) on the culture of Daphnia magna Straus. The natural mortality of D. magna is described by the Gompertz equation. One of the parameters of the equation related to daily increase of mortality is very stable, and we suggest monitoring its constancy as a sign of the health of D. magna culture. Seeding density of crustaceans affects both the fertility of species and their mortality. We observed a high degree of compensation for the natural death of adults with increasing fertility for groups of 10 and 25 species living in 1 L of water; the current population density of D. magna regulates the birth rate of juveniles. If the density is 50 individuals/L, the compensatory effect is reduced. Keeping Daphnia in small groups (for example, 10 individuals) and an increase in temperature from 20 to 25 °C reduces the average life expectancy. Therefore, when choosing a test protocol to determine chronic toxicity, it is important to pay attention to the seeding density of Daphnia, the optimal value being approximately 25 individuals/L. Sensitivity of D. magna depends on the season: it is maximal in winter and minimal in spring and summer. In addition, crustaceans’ sensitivity increases when they are kept in water with low content of natural salts. Environ Toxicol Chem 2018;37:376–384. © 2017 SETAC
Long‐term outcome of 18F‐fluorodeoxyglucose‐positron emission tomography‐guided dose painting for head and neck cancer: Matched case‐control study
Authors: Berwouts Dieter , Madani Indira , Duprez Frédéric , Olteanu AnaMaria Luiza , Vercauteren Tom , Boterberg Tom , Deron Philippe , Bonte Katrien , Huvenne Wouter , De Neve Wilfried , Goethals Ingeborg
Published: August 2017

Background

The purpose of this study was to report the long‐term outcome of 18F‐fluorodeoxyglucose‐positron emission tomography (18F‐FDG‐PET)‐guided dose painting for head and neck cancer in comparison to conventional intensity‐modulated radiotherapy (IMRT) in a matched case‐control study.

Methods

Seventy‐two patients with nonmetastatic head and neck cancer treated with dose painting were compared with 72 control patients matched on tumor site and T classification. Either 18F‐FDG‐PET‐guided dose painting by contour (DPBC) or voxel intensity‐based dose painting by number (DPBN) was performed; control patients underwent standard IMRT. A total median dose to the dose‐painted target was 70.2‐85.9 Gy/30‐32 fractions versus 69.1 Gy/32 fractions with conventional IMRT. In 31 patients, dose painting was adapted to per‐treatment changes in the tumor and organs‐at‐risk (OAR).

Results

Median follow‐up in living dose‐painting and control patients was 87.7 months (range 56.1‐119.3) and 64.8 months (range 46.3‐83.4), respectively. Five‐year local control rates in the dose‐painting patients were 82.3% against 73.6% in the control (P = .36); in patients treated to normalized isoeffective doses >91 Gy (NID2Gy) local control reached 85.7% at 5 years against 73.6% in the control group (P =.39). There was no difference in regional (P = .82) and distant control (P = .78). Five‐year overall and disease‐specific survival rates were 36.3% versus 38.1% (P = .50) and 56.5% versus 51.7% (P = .72), respectively. A half of the dose‐painting patients developed acute grade ≥3 dysphagia (P = .004). Late grade 4 mucosal ulcers at the site of dose escalation in 9 of 72 patients was the most common severe toxicity with dose painting versus 3 of 72 patients with conventional IMRT (P = .11). Patients in the dose‐painting group had increased rates of acute and late dysphagia (P = .004 and P = .005).

Conclusion

Dose‐painting strategies can be used to increase dose to specific tumor subvolumes. Five‐year local, regional, and distant control rates are comparable with patients treated with conventional IMRT. Volume and intensity of dose escalation should be further tailored, given the possible increase in severe acute and chronic toxicity. Adapting treatment and decreasing dose to the swallowing structures might contribute to lower toxicity rates when applied in smaller tumor volumes. Whether adaptive DPBN can significantly improve outcomes is currently being investigated in a novel clinical trial.
Benefits of initial CT staging before sentinel lymph node biopsy in patients with head and neck cutaneous melanoma
Authors: Hafström Anna , Silfverschiöld Maria , Persson Simon S. , Kanne Michelle , Ingvar Christian , Wahlberg Peter , Romell Anton , Greiff Lennart
Published: August 2017

Background

The value of CT at the time of diagnosis for patients with cutaneous head and neck melanoma clinically asymptomatic for metastatic disease is unclear.

Methods

A retrospective medical chart review was performed on 198 consecutive patients identified with primary T1b‐T4b head and neck melanoma clinically asymptomatic for metastatic disease referred for sentinel lymph node biopsy procedures between 2004 and 2014.

Results

Initial CTs identified clinically occult melanoma metastases in 8.1% and advanced second primary tumors in 3.5% of patients. CT findings were false‐negative in 1% and false‐positive in 6% of patients. Overall survival (OS) for patients with true‐positive CT findings was lower than for the other patients (P < .001).

Conclusion

CT imaging when staging patients with head and neck melanoma seems to identify more metastases than has been reported for melanoma at other sites. Preoperative CTs decreased the number of sentinel lymph node biopsy (SLNBs), thus avoiding the stress and cost of this surgical procedure in 12% of patients.
Partial nephrectomy margin imaging using structured illumination microscopy
Authors: Wang Mei , Tulman David B. , Sholl Andrew B. , Mandava Sree H. , Maddox Michael M. , Lee Benjamin R. , Quincy Brown J.
Published: August 2017

Partial nephrectomy (PN) is the recommended procedure over radical nephrectomy (RN) for patients with renal masses less than 4 cm in diameter (Stage T1a). Patients with less than 4 cm renal masses can also be treated with PN, but have a higher risk for positive surgical margins (PSM). PSM, when present, are indicative of poor clinical outcomes. The current gold‐standard histopathology method is not well‐suited for the identification of PSM intraoperatively due to processing time and destructive nature. Here, video‐rate structured illumination microscopy (VR‐SIM) was investigated as a potential tool for PSM detection during PN. A clinical image atlas assembled from ex vivo renal biopsies provided diagnostically useful images of benign and malignant kidney, similar to permanent histopathology. VR‐SIM was then used to image entire parenchymal margins of tumor resection covering up to >1800× more margin surface area than standard histology. Aided by the image atlas, the study pathologist correctly classified all parenchymal margins as negative for PSM with VR‐SIM, compared to standard postoperative pathology. The ability to evaluate large surgical margins in a short time frame with VR‐SIM may allow it to be used intraoperatively as a “safety net” for PSM detection, allowing more patients to undergo PN over RN.
Instanton rate constant calculations close to and above the crossover temperature
Authors: McConnell Sean , Kästner Johannes
Published: August 2017

Canonical instanton theory is known to overestimate the rate constant close to a system‐dependent crossover temperature and is inapplicable above that temperature. We compare the accuracy of the reaction rate constants calculated using recent semi‐classical rate expressions to those from canonical instanton theory. We show that rate constants calculated purely from solving the stability matrix for the action in degrees of freedom orthogonal to the instanton path is not applicable at arbitrarily low temperatures and use two methods to overcome this. Furthermore, as a by‐product of the developed methods, we derive a simple correction to canonical instanton theory that can alleviate this known overestimation of rate constants close to the crossover temperature. The combined methods accurately reproduce the rate constants of the canonical theory along the whole temperature range without the spurious overestimation near the crossover temperature. We calculate and compare rate constants on three different reactions: H in the Müller–Brown potential, methylhydroxycarbene → acetaldehyde and H2 + OH → H + H2O. © 2017 Wiley Periodicals, Inc.
Ultrastructure and distribution of antennal sensilla of the chilli thripsScirtothrips dorsalishood (Thysanoptera: Thripidae)
Authors: Zhu Wenjing , Zhou Shihao , Wang Shijie , Han Dongyin , Chen Junyu , Fu Yueguan
Published: August 2017

The chilli thrips,Scirtothrips dorsalisHood, is a serious pest of numerous important vegetable and ornamental crops. Various signals, especially phytochemical cues, determine the behavior of the phytophagous thrips at host selection. The sensory abilities ofS. dorsalisare poorly understood although the antennae of adult are known to possess important sensory structures in orther insects. In this study, the morphology, distribution, and ultrastructure of the antennal sensilla of theS. dorsaliswere examined by using scanning and transmission electron microscopy. Microscopy observations revealed that adult male and femaleS. dorsalispossess filiform antennae. Each antenna comprises a scape, a pedicel, and a flagellum composed of six segments without clear sexual dimorphism in the number and distribution of antennal sensilla. The scape and pedicel exhibit Böhm's bristles, sensilla chaetica, and sensilla campaniform. The external structures of these organs reveal their mechanosensory function. In the flagellum, the most represented sensilla are the multiporous sensilla basiconica, which can be divided into three types of single‐walled olfactory sensilla; three types of sensilla chaetica with mechanosensory and gustatory functions; sensilla coeloconica, which possess hollow cuticular spoke channels and represent double‐walled olfactory sensilla; sensilla capitula and sensilla cavity with thermo‐hygrosensory functions; and aporous sensilla trichodea with smooth cuticula and mechanosensory function. The putative function of described sensilla is discussed in ralation to host plant selection behavior ofS. dorsalis.
Indications and techniques of biliary drainage for acute cholangitis in updated Tokyo Guidelines 2018
Authors: Mukai Shuntaro , Itoi Takao , Baron Todd H. , Takada Tadahiro , Strasberg Steven M. , Pitt Henry A. , Ukai Tomohiko , Shikata Satoru , Teoh Anthony Yuen Bun , Kim Myung‐Hwan , Kiriyama Seiki , Mori Yasuhisa , Miura Fumihiko , Chen Miin‐Fu , Lau Wan Yee , Wada Keita , Supe Avinash Nivritti , Giménez Mariano Eduardo , Yoshida Masahiro , Mayumi Toshihiko , Hirata Koichi , Sumiyama Yoshinobu , Inui Kazuo , Yamamoto Masakazu
Published: August 2017

The Tokyo Guidelines 2013 (TG13) include new topics in the biliary drainage section. From these topics, we describe the indications and new techniques of biliary drainage for acute cholangitis with videos. Recently, many novel studies and case series have been published across the world, thus TG13 need to be updated regarding the indications and selection of biliary drainage based on published data. Herein, we describe the latest updated TG13 on biliary drainage in acute cholangitis with meta‐analysis. The present study showed that endoscopic transpapillary biliary drainage regardless of the use of nasobiliary drainage or biliary stenting, should be selected as the first‐line therapy for acute cholangitis. In acute cholangitis, endoscopic sphincterotomy (EST) is not routinely required for biliary drainage alone because of the concern of post‐EST bleeding. In case of concomitant bile duct stones, stone removal following EST at a single session may be considered in patients with mild or moderate acute cholangitis except in patients under anticoagulant therapy or with coagulopathy. We recommend the removal of difficult stones at two sessions after drainage in patients with a large stone or multiple stones. In patients with potential coagulopathy, endoscopic papillary dilation can be a better technique than EST for stone removal. Presently, balloon enteroscopy‐assisted endoscopic retrograde cholangiopancreatography (BE‐ERCP) is used as the first‐line therapy for biliary drainage in patients with surgically altered anatomy where BE‐ERCP expertise is present. However, the technical success rate is not always high. Thus, several studies have revealed that endoscopic ultrasonography‐guided biliary drainage (EUS‐BD) can be one of the second‐line therapies in failed BE‐ERCP as an alternative to percutaneous transhepatic biliary drainage where EUS‐BD expertise is present.
Complete degradation of dimethyl phthalate by a Comamonas testosterone strain
Authors: Li Jing , Luo Feng , Chu Dian , Xuan Huanling , Dai Xianzhu
Published: August 2017

A Comamonas testosterone bacterial strain, named as DB‐7, capable of utilizing dimethyl phthalate (DMP) as sole carbon source and energy for growth was isolated from soil with plastic film mulching by an enrichment culture technique. This bacterium was identified as C. testosterone by 16S rRNA sequence analysis and phospholipid fatty acid profile. DB‐7 could degrade more than 99% of 450 mg L−1 DMP within 14 hours, and degraded DMP of different concentrations rapidly. The optimal degradation temperature and pH were 30–35 °C and pH 9.0, respectively. The degradation rate of DMP was positively related to inoculum volume of the bacterium. The result of HPLC and LC/MS analysis of metabolic products indicated that the major degrading intermediates were mono‐methyl phthalate (MMP) and phthalic acid (PA) during the degradation of DMP by DB‐7. Partial sequences of three genes involved in PA metabolism were detected in DB‐7, and the expression of phthalate 4, 5‐dioxygenase was drastically induced in the presence of DMP and PA. DB‐7 is promising to be applied to DMP bioremediation because of its high degrading efficiency.