bluuebunny/crossref_metadata_2025 huggingface dataset:
Bifunctional MOF‐Derived Carbon Photonic Crystal Architectures for Advanced Zn–Air and Li–S Batteries: Highly Exposed Graphitic Nitrogen Matters
Authors: Yang Meijia , Hu Xuanhe , Fang Zhengsong , Sun Lu , Yuan Zhongke , Wang Shuangyin , Hong Wei , Chen Xudong , Yu Dingshan
Published: July 2017

Nitrogen‐rich porous carbons (NPCs) are the leading cathode materials for next‐generation Zn–air and Li–S batteries. However, most existing NPC suffers from insufficient exposure and harnessing of nitrogen‐dopants (NDs), constraining the electrochemical performance. Herein, by combining silica templating with in situ texturing of metal–organic frameworks, a new bifunctional 3D nitrogen‐rich carbon photonic crystal architecture of simultaneously record‐high total pore volume (13.42 cm3 g−1), ultralarge surface area (2546 m2 g−1), and permeable hierarchical macro‐meso‐microporosity is designed, enabling sufficient exposure and accessibility of NDs. Thus, when used as cathode catalysts, the Zn–air battery delivers a fantastic capacity of 770 mAh gZn−1 at an unprecedentedly high rate of 120 mA cm−2, with an ultrahigh power density of 197 mW cm−2. When hosting 78 wt% sulfur, the Li–S battery affords a high‐rate capacity of 967 mAh g−1 at 2 C, with superb stability over 1000 cycles at 0.5 C (0.054% decay rate per cycle), comparable to the best literature value. The results prove the dominant role of highly exposed graphitic‐N in boosting both cathode performances.
Unprecedented Homoleptic Bis‐Tridentate Iridium(III) Phosphors: Facile, Scaled‐Up Production, and Superior Chemical Stability
Authors: Lin Jun , Wang Yang , Gnanasekaran Premkumar , Chiang Yu‐Cheng , Yang Chun‐Chieh , Chang Chih‐Hao , Liu Shih‐Hung , Lee Gene‐Hsiang , Chou Pi‐Tai , Chi Yun , Liu Shun‐Wei
Published: July 2017

Bis‐tridentate Ir(III) metal complexes are expected to show great potential in organic light‐emitting diode (OLED) applications due to the anticipated, superb chemical and photochemical stability. Unfortunately, their exploitation has long been hampered by lack of adequate methodology and with inferior synthetic yields. This hurdle can be overcome by design of the first homoleptic, bis‐tridentate Ir(III) complex [Ir(pzpyph)(pzHpyph)] (1), for which the abbreviation (pzpyph)H (or pzHpyph) stands for the parent 2‐pyrazolyl‐6‐phenyl pyridine chelate. After that, methylation and double methylation of 1 afford the charge‐neutral Ir(III) complex [Ir(pzpyph)(pzMepyph)] (2) and cationic complex [Ir(pzMepyph)2][PF6] (3), while deprotonation of 1 gives formation of anionic [Ir(pzpyph)2][NBu4] (4), all in high yields. These bis‐tridentate Ir(III) complexes 2–4 are highly emitted in solution and solid states, while the charge‐neutral 2 and corresponding t‐butyl substituted derivative [Ir(pzpyBuph)(pzMepyBuph)] (5) exhibit superior photostability versus the tris‐bidentate references [Ir(ppy)2(acac)] and [Ir(ppy)3] in toluene under argon, making them ideal OLED emitters. For the track record, phosphor 5 gives very small efficiency roll‐off and excellent overall efficiencies of 20.7%, 66.8 cd A−1, and 52.8 lm W−1 at high brightness of 1000 cd m−2. These results are expected to inspire further studies on the bis‐tridentate Ir(III) complexes, which are judged to be more stable than their tris‐bidentate counterparts from the entropic point of view.
Edge Sites with Unsaturated Coordination on Core–Shell Mn3O4@MnxCo3−xO4 Nanostructures for Electrocatalytic Water Oxidation
Authors: Hu Congling , Zhang Lei , Zhao Zhi‐Jian , Luo Jun , Shi Jing , Huang Zhiqi , Gong Jinlong
Published: July 2017

Transition‐metal oxides are extensively investigated as efficient electrocatalysts for the oxygen evolution reaction (OER). However, large‐scale applications remain challenging due to their moderate catalytic activity. Optimized regulation of surface states can lead to improvement of catalytic properties. Here, the design of Mn@CoxMn3−xO4 nanoparticles with abundant edge sites via a simple seed‐mediated growth strategy is described. The unsaturated coordination generated on the edge sites of CoxMn3−xO4 shells makes a positive contribution to the surface‐structure tailoring. Density functional theory calculations indicate that the edge sites with unsaturated coordination exhibit intense affinity for OH− in the alkaline electrolyte, which greatly enhances the electrochemical OER performance of the catalysts. The resulting Mn@CoxMn3−xO4 catalysts yield a current density of 10 mA cm−2 at an overpotential of 246 mV and a relatively low Tafel slope of 46 mV dec−1. The successful synthesis of these metal oxides nanoparticles with edge sites may pave a new path for rationally fabricating efficient OER catalysts.
Base‐Promoted [3+2]‐Annulation of Oxime Esters and Aldehydes for Rapid Isoxazoline Formation
Authors: Huang Huawen , Li Feifei , Xu Zhenhua , Cai Jinhui , Ji Xiaochen , Deng Guo‐Jun
Published: July 2017

A base‐promoted [3+2]‐annulation of ketoxime esters and aldehydes is disclosed for the facile and rapid synthesis of 3,5‐disubstituted and 3,4,5‐trisubstituted isoxazolines. The key to our success is the pivalate leaving group of the oxime substrates, combined with cesium carbonate as promoter. This chemistry allows the assembly of a vast array of isoxazoline derivatives under simple base conditions in a method complementary to the classic isoxazoline formation via [3+2]‐dipolar cycloaddition of nitrile oxides and olefins. It also represents a new reaction pattern involving electrophilic amination/N–O bond substitution.

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Complete carbon analysis of sulfur‐containing mixtures using postcolumn reaction and flame ionization detection
Authors: Beach Connor A. , Joseph Kristeen E. , Dauenhauer Paul J. , Spanjers Charles S. , Jones Andrew J. , Mountziaris Triantafillos J.
Published: July 2017

Quantitative analysis of complex mixtures containing hundreds‐to‐thousands of organic compounds rich in heteroatoms, including oxygen, sulfur, and nitrogen, is a major challenge in the fuel, food, and chemical industries. In this work, a two‐stage (oxidation and methanation) catalytic process in a 3‐D–printed metal microreactor was evaluated for its capability to convert sulfur‐containing organic compounds to methane. The microreactor was inserted into a gas chromatograph between the capillary column and flame ionization detector. Catalytic conversion of all sulfur‐containing analytes to methane enabled carbon quantification without calibration, by the method identified as “quantitative carbon detection” or QCD. Quantification of tetrahydrothiophene, dimethyl sulfoxide, diethyl sulfide, and thiophene indicated complete conversion to methane at 450°C. Long‐term performance of a commercial microreactor was evaluated for 2000 consecutive injections of sulfur‐containing organic analytes. The sulfur processing capacity of the microreactor was identified experimentally, after which reduced conversion to methane was observed. © 2017 American Institute of Chemical Engineers AIChE J, 63: 5438–5444, 2017
Formation of liquid–liquid slug flow in a microfluidic T‐junction: Effects of fluid properties and leakage flow
Authors: Yao Chaoqun , Liu Yanyan , Xu Chao , Zhao Shuainan , Chen Guangwen
Published: July 2017

Characteristics of liquid–liquid slug flow are investigated in a microchannel with focus on the leakage flow that bypasses droplets through channel gutters. The results show that the leakage flow rate varies in a range of 10.7–53.5% and 8.3–30.9% of the feed flow rate, during the droplet formation (i.e., at T‐junction) and downstream flow (i.e., in the main channel), respectively, which highly depends on Ca number and wetting condition. Empirical correlations are proposed to predict them for perfectly and partially wetting conditions. Leakage flow contribution is further used to improve the Garstecki model for size scaling in order to extend its suitability for both squeezing and shearing regimes. The instantaneous flow rates of the immiscible phases are found to fluctuate periodically with the formation cycles, but in opposite behavior. The effect of the presence of leakage flow on such fluctuation are investigated and compared with gas–liquid systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 346–357, 2018
New common program requirements for the resident physician workforce and the omission of strategic napping: A missed opportunity
Authors: Shnayder Michelle M. , St Onge Joan E. , Caban‐Martinez Alberto J.
Published: July 2017

Objectives

Napping has known benefits for fatigue mitigation and improved alertness. However the Accreditation Council for Graduate Medical Education (ACGME) New Common Program Requirements recently removed the 16 h work limit for PGY1 residents and removed any suggestions of napping.

Methods

We utilized a cross‐sectional study design to administer a 44‐item questionnaire in June 2016 to 858 residents and fellows at one large urban academic medical center. We assessed: 1) resident physician sentiment of work environment supportiveness for napping at work; and 2) agreement with 2011 ACGME guidelines on workweek hour limitations and strategic napping recommendations.

Results

While 89% of residents reported access to an on‐call room at work, only 20% felt their work environment supported a culture of napping while at work. Over 76% expressed agreement with the 2011 ACGME work‐hour restrictions.

Conclusions

Strategies to support napping and well‐being within the resident physician workforce and organizational setting are warranted.
Lung cancer in a patient with predominantly short tremolite fibers in his lung
Authors: Kohyama Norihiko , Fujiki Masaaki , Kishimoto Takumi , Morinaga Kenji
Published: July 2017

The carcinogenicity of short tremolite fibers in human has not been cleared and has been argued hitherto. A lung cancer patient had worked at a gabbro quarry. Particles isolated from the excised lung parenchyma of the patient were measured for asbestos bodies (ABs) and asbestos fibers (AFs). The concentrations of ABs were 3964 AB/g dry lung, and AFs were 5.60 × 106 fibers/g dry lung (>5 um in length) and 22.5 × 106 fibers/g dry lung (>1 um in length). AFs were mostly tremolite fibers and under 7 um in length (mean length 4.0 um, standard deviation 2.8 um). Almost all fibers were <10 um in length and an aspect ratio (AR) of <20:1 and ≥3:1. The patient had never smoked. His wife, who had worked with him in the quarry, had died of pleural mesothelioma. This study strongly indicates that such short tremolite fibers will induce lung cancer and possibly mesothelioma in human.
Ultrasound‐Assisted Synthesis and Antioxidant Activity of 3‐Selanyl‐1 H‐indole and 3‐Selanylimidazo[1,2‐a]pyridine Derivatives
Authors: Vieira Beatriz M. , Thurow Samuel , da Costa Monaliza , Casaril Angela M. , Domingues Micaela , Schumacher Ricardo F. , Perin Gelson , Alves Diego , Savegnago Lucielli , Lenardão Eder J.
Published: July 2017

A simple and rapid method for the selective synthesis of 3‐(organylselanyl)‐1 H‐indoles and 3‐(organylselanyl)imidazo[1,2‐a]pyridines catalyzed by CuI/SeO2 under ultrasound irradiation was developed. This protocol employs a diverse range of 1 H‐indoles or imidazo[1,2‐a]pyridines and diorganyl diselenides to afford the corresponding products selectively in good to excellent yields. Moreover, the antioxidant activity of these compounds was evaluated by using a wide range of in vitro assays, such as 2‐azinobis‐3‐ethylbenzothiazoline‐6‐sulfonic acid (ABTS), 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical, ferric ion reducing antioxidant power (FRAP), and inhibition of reactive species formation in mice cortex. The bioassays revealed that both classes of the newly synthesized organoselenium compounds present antioxidant activity, with emphasis on the 3‐(organylselanyl)‐1 H‐indoles. This pharmacological activity opens a wide range of biological applications where the reduction of oxidative stress is essential.
Enzyme‐Responsive LipoCEST Agents: Assessment of MMP‐2 Activity by Measuring the Intra‐liposomal Water1H NMR Shift
Authors: Ferrauto Giuseppe , Di Gregorio Enza , Ruzza Marta , Catanzaro Valeria , Padovan Sergio , Aime Silvio
Published: July 2017

Mobile proton‐containing solutes can be detected by MRI by the chemical exchange saturation transfer (CEST) method. CEST sensitivity is dramatically enhanced by using, as exchanging protons, the water molecules confined inside liposomes, shifted by a paramagnetic shift reagent. The chemical shift of the intraliposomal water resonance (δIL) is affected by the overall shape of the supramolecular system. δILof a spherical LipoCEST acts as a sensitive reporter of the distribution of streptavidin proteins anchored at the liposome surface by biotinylated phospholipids. This finding prompted the design of a MMP‐2 responsive LipoCEST agent as the streptavidin moieties can be released from the liposome surfaces when a properly tailored enzyme‐cleavable peptide is inserted on the phospholipids before the terminal biotin residues. δILreports on the overall changes in the supramolecular architecture associated to the cleavage carried out by MMP‐2.
Forging Fluorine‐Containing Quaternary Stereocenters by a Light‐Driven Organocatalytic Aldol Desymmetrization Process
Authors: Cuadros Sara , Dell'Amico Luca , Melchiorre Paolo
Published: July 2017

Reported herein is a light‐triggered organocatalytic strategy for the desymmetrization of achiral 2‐fluoro‐substituted cyclopentane‐1,3‐diketones. The chemistry is based on an intermolecular aldol reaction of photochemically generated hydroxy‐o‐quinodimethanes and simultaneously forges two adjacent fully substituted carbon stereocenters, with one bearing a stereogenic carbon–fluorine unit. The method uses readily available substrates, a simple chiral organocatalyst, and mild reaction conditions to afford an array of highly functionalized chiral 2‐fluoro‐3‐hydroxycyclopentanones.
Electron acceleration and small‐scale coherent structure formation by an Alfvén wave propagating in coronal interplume region
Authors: Daiffallah K. , Mottez F.
Published: July 2017

We use the 2.5‐D electromagnetic particle‐in‐cell simulation code to investigate the acceleration of electrons in solar coronal holes through the interaction of Alfvén waves with an interplume region. The interplume is modeled by cavity density gradients that are perpendicular to the background magnetic field. The aim is to help explain the observation of suprathermal electrons under a relatively quiet Sun. Simulations show that Alfvén waves interacting with the interplume region give rise to a strong local electric field that accelerates electrons in the direction parallel to the background magnetic field. Suprathermal electron beams and small‐scale coherent structures are observed within interplume of strong density gradients. These features result from the nonlinear evolution of the electron beam plasma instability.
Decision‐theoretic designs for a series of trials with correlated treatment effects using the Sarmanov multivariate beta‐binomial distribution
Authors: Hee Siew Wan , Parsons Nicholas , Stallard Nigel
Published: July 2017

The motivation for the work in this article is the setting in which a number of treatments are available for evaluation in phase II clinical trials and where it may be infeasible to try them concurrently because the intended population is small. This paper introduces an extension of previous work on decision‐theoretic designs for a series of phase II trials. The program encompasses a series of sequential phase II trials with interim decision making and a single two‐arm phase III trial. The design is based on a hybrid approach where the final analysis of the phase III data is based on a classical frequentist hypothesis test, whereas the trials are designed using a Bayesian decision‐theoretic approach in which the unknown treatment effect is assumed to follow a known prior distribution. In addition, as treatments are intended for the same population it is not unrealistic to consider treatment effects to be correlated. Thus, the prior distribution will reflect this. Data from a randomized trial of severe arthritis of the hip are used to test the application of the design. We show that the design on average requires fewer patients in phase II than when the correlation is ignored. Correspondingly, the time required to recommend an efficacious treatment for phase III is quicker.
Investigation of the interaction of aurantio‐obtusin with human serum albumin by spectroscopic and molecular docking methods
Authors: Liu Jianming , Yan Xuyang , Yue Yuanyuan , Zhao Shufang
Published: July 2017

The interaction between human serum albumin (HSA) and aurantio‐obtusin was investigated by spectroscopic techniques combined with molecular docking. The Stern–Volmer quenching constants (KSV) decreased from 8.56 × 105 M−1 to 5.13 × 105 M−1 with a rise in temperatures from 289 to 310 K, indicating that aurantio‐obtusin produced a static quenching of the intrinsic fluorescence of HSA. Time‐resolved fluorescence studies proved again that the static quenching mechanism was involved in the interaction. The sign and magnitude of the enthalpy change as well as the entropy change suggested involvement of hydrogen bonding and hydrophobic interaction in aurantio‐obtusin–HSA complex formation. Aurantio‐obtusin binding to HSA produced significant alterations in secondary structures of HSA, as revealed from the time‐resolved fluorescence, Fourier transform infrared (FT‐IR) spectroscopy, three‐dimensional (3D) fluorescence and circular dichroism (CD) spectral results. Molecular docking study and site marker competitive experiment confirmed aurantio‐obtusin bound to HSA at site I (subdomain IIA).
Sex differences in mortality after abdominal aortic aneurysm repair in the UK
Authors: Sidloff D A , Saratzis A , Sweeting M J , Michaels J , Powell J T , Thompson S G , Bown M J
Published: July 2017

Background

The UK abdominal aortic aneurysm (AAA) screening programmes currently invite only men for screening because the benefit in women is uncertain. Perioperative risk is critical in determining the effectiveness of screening, and contemporary estimates of these risks in women are lacking. The aim of this study was to compare mortality following AAA repair between women and men in the UK.

Methods

Anonymized data from the UK National Vascular Registry (NVR) for patients undergoing AAA repair (January 2010 to December 2014) were analysed. Co-variables were extracted for analysis by sex. The primary outcome measure was in-hospital mortality. Secondary outcome measures included mortality by 5-year age groups and duration of hospital stay. Logistic regression was performed to adjust for age, calendar time, AAA diameter and smoking status. NVR-based outcomes were checked against Hospital Episode Statistics (HES) data.

Results

A total of 23 245 patients were included (13·0 per cent women). Proportionally, more women than men underwent open repair. For elective open AAA repair, the in-hospital mortality rate was 6·9 per cent in women and 4·0 per cent in men (odds ratio (OR) 1·48, 95 per cent c.i. 1·08 to 2·02; P = 0·014), whereas for elective endovascular AAA repair it was 1·8 per cent in women and 0·7 per cent in men (OR 2·86, 1·72 to 4·74; P < 0·001); the results in HES were similar. For ruptured AAA, there was no sex difference in mortality within the NVR; however, in HES, for ruptured open AAA repair, the in-hospital mortality rate was higher in women (33·6 versus 27·1 per cent; OR 1·36, 1·16 to 1·59; P < 0·001).

Conclusion

Women have a higher in-hospital mortality rate than men after elective AAA repair even after adjustment. This higher mortality may have an impact on the benefit offered by any screening programme offered to women.
Average treatment effect of hepatic resection versus locoregional therapies for hepatocellular carcinoma
Authors: Cucchetti A , Mazzaferro V , Pinna A D , Sposito C , Golfieri R , Serra C , Spreafico C , Piscaglia F , Cappelli A , Bongini M , Cucchi M , Cescon M
Published: July 2017

Background

When comparing the efficacy of surgical and non-surgical therapies for hepatocellular carcinoma (HCC), a major limitation is the causal inference problem. This concerns the impossibility of seeing both outcomes of two different treatments for the same individual at the same time because one is inevitably missing. This aspect can be addressed methodologically by estimating the so-called average treatment effect (ATE).

Methods

To estimate the ATE of hepatic resection over locoregional therapies for HCC, data from patients treated in two tertiary care settings between August 2000 and December 2014 were used to obtain counterfactual outcomes using an inverse probability weight survival adjustment.

Results

A total of 1585 patients were enrolled: 815 underwent hepatic resection, 337 radiofrequency ablation (RFA) and 433 transarterial chemoembolization (TACE). The option of operating on all patients who had tumour ablation returned an ATE of +9·8 months for resection (effect size 0·111; adjusted P = 0·064). The option of operating on all patients who had TACE returned an ATE of +27·9 months (effect size 0·383; adjusted P < 0·001). The ATE of surgery was negligible in patients undergoing ablation for very early HCCs (effect size 0·027; adjusted P = 0·627), independently of albumin–bilirubin (ALBI) grade; or in patients with ALBI liver function grade 2 (effect size 0·083; adjusted P = 0·213), independently of tumour stage. In all other instances, the ATE of surgery was notably greater. Operating on patients who had TACE with multinodular HCC beyond the Milan criteria resulted in a mild ATE (effect size 0·140; adjusted P = 0·037).

Conclusion

ATE estimation suggests that hepatic resection is a better treatment option than ablation and TACE in patients with HCC.
‘No one ever speaks about it’: A qualitative investigation exploring the experiences of multilingual counsellors in practice
Authors: Johal Jindy
Published: July 2017

Aim

To explore and understand the experiences of counsellors who were trained in English, but used another language when counselling clients who did not speak English or had limited English language proficiency. Although multilingual counselling is growing, this had seldom been specifically researched, with the experiences of counsellors being even more neglected.

Method

This research adopted a qualitative methodology which involved interviewing 11 participants trained in different modalities, using different languages with varied levels of experience of counselling in another language, to obtain a range of narratives. Interviews were audio recorded, followed by verbatim transcriptions and thematic analysis.

Findings

The study found participants had not previously had an opportunity to discuss their experiences of offering multilingual counselling. A discussion around counselling in a language other than English had not taken place during training, in their workplace, in supervision or with peers. They described many difficulties that influenced client work. Participants reported feeling isolated, tired and bearing full responsibility for their work. They described significant differences between counselling in English and other languages, with the clients of the latter receiving a less useful service than English speaking clients.

Discussion

An exploration of the research findings alongside contemporary literature highlights the possibility that further training and support may be needed for multilingual counsellors. Recommendations for service providers, future research and training are suggested.
Highly Enantioselective Production of Chiral Secondary Alcohols with Candida zeylanoides as a New Whole Cell Biocatalyst
Authors: Şahin Engin , Dertli Enes
Published: July 2017

The increasing demand for biocatalysts in synthesizing enantiomerically pure chiral alcohols results from the outstanding characteristics of biocatalysts in reaction, economic, and ecological issues. Herein, fifteen yeast strains belonging to three food originated yeast species Candida zeylanoides, Pichia fermentans, and Saccharomyces uvarum were tested for their capability for asymmetric reduction of acetophenone to 1‐phenylethanol as biocatalysts. Of these strains, C. zeylanoides P1 showed an effective asymmetric reduction ability. Under optimized conditions, substituted acetophenones were converted to corresponding optically active secondary alcohols in up to 99% enantiomeric excess and at high yields. The preparative scale asymmetric bioreduction of 4‐nitroacetophenone (1m) by C. zeylanoides P1 gave (S)‐1‐(4‐nitrophenyl)ethanol (2m) with 89% yield and > 99% enantiomeric excess. Compound 2m has been obtained in an enantiomerically pure and inexpensive form. Additionally, these results indicate that C. zeylanoides P1 is a promising biocatalyst for the synthesis of chiral alcohols in industry.
Transesterification of Canola Oil to Biodiesel Using CaO/Talc Nanopowder as a Mixed Oxide Catalyst
Authors: Maleki Hesam , Kazemeini Mohammad , Bastan Farzad
Published: July 2017

A series of heterogeneous catalysts including different molar ratios of CaO/talc was synthesized to study the transesterification reaction of canola oil and methanol under different reaction conditions. Characterization and kinetic results revealed that the activity of this catalyst was enhanced due to the increase of CaO/talc molar ratio value leading to an improvement in the biodiesel production. Moreover, the effect of various parameters on the activity of the undertaken catalysts was studied in order to determine the optimum process conditions. Leaching measurements and the durability of the CaO/talc catalyst under several reaction cycles were evaluated and proved it to be a stable catalyst.
Activity Hysteresis during Cyclic Temperature‐Programmed Reactions in the Partial Oxidation of Acrolein to Acrylic Acid
Authors: Knoche Stefan , Heid Maurice , Gora Niklas , Ohlig Dominik , Drochner Alfons , Vogel Herbert , Etzold Bastian J. M.
Published: July 2017

Oxidation of acrolein to acrylic acid on a Mo/V/W mixed oxide catalyst was studied by transient (cyclic temperature‐programmed (TP)) as well as steady‐state methods. TP reactions (TPReactions) exhibit an activity hysteresis of the catalyst with respect to temperature. As a result of the steady‐state measurements, the activity hysteresis is not related to multiple steady states and is exclusively a transient phenomenon. Generally, the dynamics of bulk oxygen plays a key role leading to a reversible oxidation/reduction of the catalyst surface which influences the activity. This means the bulk acts as oxygen buffer. In this context, a reaction model, which involves the participation of bulk oxygen, was deduced and verified by modeling.
Meniscus Asymmetry and Chemo‐Marangoni Convection in Capillaries
Authors: Eckert Kerstin , Shi Ying , Seidel Kirsten , Schwarzenberger Karin
Published: July 2017

A liquid‐liquid system inside a capillary in which an interfacial reaction leads to in situ production of a surfactant was studied experimentally. The resulting chemo‐Marangoni convection induces periodic spreading‐dewetting cycles in laboratory experiments. By selected experiments in microgravity, the individual phenomena of the system dynamics could be isolated. The spreading‐dewetting cycles result from a complex interplay between the decrease in interfacial tension due to the production of surfactant, the chemo‐Marangoni convection, and the gravity‐driven deformation of the meniscus shape.
A Simple Optoelectronic Tongue Discriminates Amino Acids
Authors: Wang Benhua , Han Jinsong , Ma Chao , Bender Markus , Seehafer Kai , Herrmann Andreas , Bunz Uwe H. F.
Published: July 2017

A self‐assembled nine‐element optoelectronic tongue consisting of a positively charged water‐soluble poly(para‐phenyleneethynylene) and three metal ions (Fe2+, Co2+, and Cu2+) at three different pH values (7, 10, and 13) discriminates all of the 20 natural amino acids in water. Unknown identification was not ideal. Addition of a highly positively charged green fluorescent protein in the presence of Fe2+, Co2+, and Cu2+ increased the unknown identification to above 86 %. Linear discriminant analysis (LDA) orders the responses according to the amino acid type, that is, hydrophobic, polar, anionic, or cationic.
Buttressing Effect as a Key Design Principle towards Highly Efficient Palladium/N‐Heterocyclic Carbene Buchwald–Hartwig Amination Catalysts
Authors: Zhang Yin , Lavigne Guy , Lugan Noël , César Vincent
Published: July 2017

The backbone substitution of the standard 1,3‐bis(2,6‐diisopropylphenyl)‐2H‐imidazol‐2‐ylidene (IPr) ligand by dimethylamino groups was previously shown to induce a dramatic improvement in the catalytic efficiency of the corresponding Pd–PEPPSI (pyridine‐enhanced pre‐catalyst preparation, stabilization, and initiation) pre‐catalysts in N‐arylation reactions. Herein, a thorough structure/activity study towards rationalizing this beneficial effect has been described. In addition to the previously reported IPr
and IPr
ligands, the new IPr
and IPr
ligands, which bear one bulkier diisopropylamino group and a combination of dimethylamino and chloro substituents, respectively, have been designed and analyzed in the study. The influence of the backbone substitution was found to be steric in origin and is related to the well‐known buttressing effect encountered in arene chemistry. The usefulness and versatility of this approach was demonstrated through the development of a highly efficient catalytic system for the challenging arylation of bulky α,α,α‐trisubstituted primary amines. The optimized system based on the [PdCl(η3‐cinnamyl)(IPr
)] or [PdCl(η3‐cinnamyl)(IPr
)] pre‐catalysts operates under unprecedented mild conditions (catalyst loadings: 0.5–2 mol %, reaction temperatures: 40–60 °C) with a wide substrate scope.
Coordination‐Driven Folding in Multi‐ZnII‐Porphyrin Arrays Constructed on a Pillar[5]arene Scaffold
Authors: Trinh Thi Minh Nguyet , Nierengarten Iwona , Ben Aziza Haifa , Meichsner Eric , Holler Michel , Chessé Matthieu , Abidi Rym , Bijani Christian , Coppel Yannick , Maisonhaute Emmanuel , Delavaux‐Nicot Béatrice , Nierengarten Jean‐François
Published: July 2017

Invited for the cover of this issue are the groups of Emmanuel Maisonhaute at Sorbonne Universités, Béatrice Delavaux‐Nicot at the Laboratoire de Chimie de Coordination (LCC) du CNRS (Université de Toulouse), and Jean‐François Nierengarten at the Université de Strasbourg. The image depicts an artistic view of the open molecular flower upon treatment with an imidazole ligand. Read the full text of the article at 10.1002/chem.201701622.
One‐Pot Synthesis of 4‐Aryl‐NH‐1,2,3‐Triazoles through Three‐Component Reaction of Aldehydes, Nitroalkanes and NaN3
Authors: Hui Rongrong , Zhao Mina , Chen Ming , Ren Zhihui , Guan Zhenghui
Published: July 2017

A one‐pot three‐component reaction of aldehydes, nitroalkanes and NaN3 for the synthesis of NH‐1,2,3‐triazoles has been developed. The reaction provides a safe, efficient and step‐economic approach for the synthesis of various NH‐1,2,3‐triazoles in good to excellent yields.
Cancer donor preferences for disposition of their biospecimens after biobank closure
Authors: Allen Samuel C. , Dixon Margie D. , Switchenko Jeffrey M. , Pentz Rebecca D.
Published: July 2017

BACKGROUND

Biobank funding is unstable and biobank administrators are concerned about loss of funding and subsequent biobank closure. Nevertheless, only a minority of biobanks have policies regarding the distribution or destruction of tissue if the biobank were to close. To the authors' knowledge, the current study is the first to report on the preferences of oncology biospecimen donors regarding the handling of their biospecimens in the event of biobank closure.

METHODS

A total of 98 biospecimen donors who were diagnosed with cancer at the Georgia Cancer Center for Excellence at Grady Memorial Hospital or the Winship Cancer Institute were interviewed concerning their preferences for the handling of their biospecimens in the event of biobank closure.

RESULTS

The majority of biospecimen donors who expressed a preference (62 of 83 donors; 75%) wanted their biological materials transferred to another biobank, specifically an academic bank or a national bank. The most unacceptable options for the handling of tissue were transfer to a for‐profit/pharmaceutical biobank (39 of 98 donors; 40%) or a biobank based outside of the United States (31 of 98 donors; 32%). Nonwhite participants were more likely to view the transfer of their tissue to a for‐profit/pharmaceutical tissue bank, international tissue bank, or a national tissue bank as unacceptable compared with white participants.

CONCLUSIONS

According to these biospecimen donors, the most acceptable options for the handling of biospecimens after biobank closure were transfer to an academic or national bank. The most objectionable options were transfer to a for‐profit/pharmaceutical biobank or a biobank based outside of the United States. These findings can be used as the basis for educational interventions directed at the public and can inform the policies of biobanks that serve oncology research. Cancer 2017;123:4648‐4652. © 2017 American Cancer Society.
High diversity in neuropeptide immunoreactivity patterns among three closely related species of Dinophilidae (Annelida)
Authors: Kerbl Alexandra , Conzelmann Markus , Jékely Gáspár , Worsaae Katrine
Published: July 2017

Neuropeptides are conserved metazoan signaling molecules, and represent useful markers for comparative investigations on the morphology and function of the nervous system. However, little is known about the variation of neuropeptide expression patterns across closely related species in invertebrate groups other than insects. In this study, we compare the immunoreactivity patterns of 14 neuropeptides in three closely related microscopic dinophilid annelids (Dinophilus gyrociliatus, D. taeniatus and Trilobodrilus axi). The brains of all three species were found to consist of around 700 somata, surrounding a central neuropil with 3–5 ventral and 2–5 dorsal commissures. Neuropeptide immunoreactivity was detected in the brain, the ventral cords, stomatogastric nervous system, and additional nerves. Different neuropeptides are expressed in specific, non‐overlapping cells in the brain in all three species. FMRFamide, MLD/pedal peptide, allatotropin, RNamide, excitatory peptide, and FVRIamide showed a broad localization within the brain, while calcitonin, SIFamide, vasotocin, RGWamide, DLamide, FLamide, FVamide, MIP, and serotonin were present in fewer cells in demarcated regions. The different markers did not reveal ganglionic subdivisions or physical compartmentalization in any of these microscopic brains. The non‐overlapping expression of different neuropeptides may indicate that the regionalization in these uniform, small brains is realized by individual cells, rather than cell clusters, representing an alternative to the lobular organization observed in several macroscopic annelids. Furthermore, despite the similar gross brain morphology, we found an unexpectedly high variation in the expression patterns of neuropeptides across species. This suggests that neuropeptide expression evolves faster than morphology, representing a possible mechanism for the evolutionary divergence of behaviors.
Tonotopic alterations in inhibitory input to the medial nucleus of the trapezoid body in a mouse model of Fragile X syndrome
Authors: McCullagh Elizabeth A. , Salcedo Ernesto , Huntsman Molly M. , Klug Achim
Published: July 2017

Hyperexcitability and the imbalance of excitation/inhibition are one of the leading causes of abnormal sensory processing in Fragile X syndrome (FXS). The precise timing and distribution of excitation and inhibition is crucial for auditory processing at the level of the auditory brainstem, which is responsible for sound localization ability. Sound localization is one of the sensory abilities disrupted by loss of the Fragile X Mental Retardation 1 (Fmr1) gene. Using triple immunofluorescence staining we tested whether there were alterations in the number and size of presynaptic structures for the three primary neurotransmitters (glutamate, glycine, and GABA) in the auditory brainstem of Fmr1 knockout mice. We found decreases in either glycinergic or GABAergic inhibition to the medial nucleus of the trapezoid body (MNTB) specific to the tonotopic location within the nucleus. MNTB is one of the primary inhibitory nuclei in the auditory brainstem and participates in the sound localization process with fast and well‐timed inhibition. Thus, a decrease in inhibitory afferents to MNTB neurons should lead to greater inhibitory output to the projections from this nucleus. In contrast, we did not see any other significant alterations in balance of excitation/inhibition in any of the other auditory brainstem nuclei measured, suggesting that the alterations observed in the MNTB are both nucleus and frequency specific. We furthermore show that glycinergic inhibition may be an important contributor to imbalances in excitation and inhibition in FXS and that the auditory brainstem is a useful circuit for testing these imbalances.
Benchmark problems for numerical treatment of backflow at open boundaries
Authors: Bertoglio Cristóbal , Caiazzo Alfonso , Bazilevs Yuri , Braack Malte , Esmaily Mahdi , Gravemeier Volker , L. Marsden Alison , Pironneau Olivier , E. Vignon‐Clementel Irene , A. Wall Wolfgang
Published: July 2017

In computational fluid dynamics, incoming velocity at open boundaries, or backflow, often yields unphysical instabilities already for moderate Reynolds numbers. Several treatments to overcome these backflow instabilities have been proposed in the literature. However, these approaches have not yet been compared in detail in terms of accuracy in different physiological regimes, in particular because of the difficulty to generate stable reference solutions apart from analytical forms. In this work, we present a set of benchmark problems in order to compare different methods in different backflow regimes (with a full reversal flow and with propagating vortices after a stenosis). The examples are implemented in FreeFem++, and the source code is openly available, making them a solid basis for future method developments.
Inverse estimation of cardiac activation times via gradient‐based optimization
Authors: Kallhovd Siri , Maleckar Mary M. , Rognes Marie E.
Published: July 2017

Computational modeling may provide a quantitative framework for integrating multiscale data to gain insight into mechanisms of heart disease, identify and test pharmacological and electrical therapy and interventions, and support clinical decisions. Patient‐specific computational cardiac models can help guide such procedures, and cardiac inverse modeling is a promising alternative to adequately personalize these models. Indeed, full cardiac inverse modeling is currently becoming computationally feasible; however, fundamental work to assess the feasibility of emerging techniques is still needed. In this study, we use a partial differential equation–constrained optimal control approach to numerically investigate the identifiability of an initial activation sequence from synthetic (partial) observations of the extracellular potential using the bidomain approximation and 2D representations of cardiac tissue. Our results demonstrate that activation times and duration of several stimuli can be recovered even with high levels of noise, that it is sufficient to sample the observations at the electrocardiogram‐relevant sampling frequency of 1 kHz, and that spatial resolutions that are coarser than the standard in electrophysiological simulations can be used. The optimization of activation times is still effective when synthetic data are generated with a different cell membrane kinetics model than optimized for. The findings thus indicate that the presented approach has potential for finding activation sequences from clinical data modalities, as an extension to existing cardiac imaging approaches.
Insights into the Hydrogen‐Atom Transfer of the Blue Aroxyl
Authors: Bächle Josua , Marković Marijana , Kelterer Anne‐Marie , Grampp Günter
Published: July 2017

An experimental and theoretical study on hydrogen‐atom transfer dynamics in the hydrogen‐bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6‐tri‐tert‐butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature‐dependent alternating line‐width effect in the continuous‐wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy‐atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post‐Hartree–Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen‐atom transfer along a parabolic reaction path caused by heavy‐atom motion.
Experimental Realization of a High‐Quality Biochemical XOR Gate
Authors: Filipov Yaroslav , Domanskyi Sergii , Wood Mackenna L. , Gamella Maria , Privman Vladimir , Katz Evgeny
Published: July 2017

We report an experimental realization of a biochemical XOR gate function that avoids many of the pitfalls of earlier realizations based on biocatalytic cascades. Inputs—represented by pairs of chemicals—cross‐react to largely cancel out when both are nearly equal. The cross‐reaction can be designed to also optimize gate functioning for noise handling. When not equal, the residual inputs are further processed to result in the output of the XOR type, by biocatalytic steps that allow for further gate‐function optimization. The quality of the realized XOR gate is theoretically analyzed.
Analysis of Reaction Processes On the Basis of the Evolution of Dynamic Orbital Forces: Examples of Cycloadditions, SN2 Substitution, Nucleophilic Addition, and Hydrogen Transposition
Authors: Chaquin Patrick , Fuster Franck
Published: July 2017

The derivative of the energy of a canonical molecular orbital (MO) [or dynamical orbital forces (DOFs)] with respect to a bond length provides a reliable index of the bonding/antibonding character of this MO on this bond. The DOFs of selected MOs as a function of the reaction coordinate were computed for a panel of model reaction mechanisms: [2+4] (Diels–Alder) cycloaddition, [2+2] cycloaddition, second‐order nucleophilic substitution (SN2), nucleophilic addition to a carbonyl group, and [1,2] hydrogen transposition. The results highlight the nature of the reorganization of the main MOs and the stage of the reaction coordinate (RC) at which it occurs. For instance, in the Diels–Alder reaction, one can identify a part of the reaction that is dominated by repulsive four‐electron interactions and another part dominated by attractive two‐electron interactions. Also, the shape of the DOF as a function of the reaction coordinate reveals the existence of avoided MO crossings and their location on the RC. Even for spontaneous reactions with monotonic variation in the potential energy, extrema of the MO energy and sudden electron rearrangements can be put into evidence. This study provides quantitative support to classical MO analyses of reactivity such as correlation diagrams and frontier approximation.
Differences in clinical intrusive thoughts between obsessive–compulsive disorder, generalized anxiety disorder, and hypochondria
Authors: Romero‐Sanchiz Pablo , Nogueira‐Arjona Raquel , Godoy‐Ávila Antonio , Gavino‐Lázaro Aurora , Freeston Mark H.
Published: July 2017

Differences and similarities between intrusive thoughts typical of obsessive–compulsive disorder, generalized anxiety disorder, and hypochondriasis are relevant for their differential diagnosis, formulation, and psychological treatment. Previous research in non‐clinical samples pointed out the relevance of some process variables, such as responsibility, guilt, or neutralization strategies. This research is aimed to investigate the differences and similarities between clinical obsessions, worries, and illness intrusions in some of these process variables. A second aim is to identify models based on these variables that could reliably differentiate between them. Three groups of patients with obsessive–compulsive disorder (n = 35; 60% women, mean age 38.57), generalized anxiety disorder (n = 36; 61.1% women, mean age 41.50), and hypochondriasis (n = 34; 70.6% women, mean age 31.59) were evaluated using the Cognitive Intrusions Questionnaire—Transdiagnostic Version (Romero‐Sanchiz, Nogueira‐Arjona, Godoy‐Ávila, Gavino‐Lázaro, & Freeston, ). The results showed that some appraisals (e.g., responsibility or egodystonicity), emotions (e.g., guilt or insecurity), neutralization strategies, and other variables (e.g., verbal content or trigger from body sensation) are relevant for the discrimination between obsessions, worries, and illness intrusions. The results also showed 3 stable models based on these variables for the discrimination between these thoughts. The implication of these results in the diagnosis, formulation, and psychological treatment of obsessive–compulsive disorder, generalized anxiety disorder, and hypochondriasis is discussed.
Flow cytometry vs optical microscopy in the evaluation of the genotoxic potential of xenobiotic compounds
Authors: Lenzi Monia , Cocchi Veronica , Hrelia Patrizia
Published: July 2017

Background

It is now recognized that mutational events play a key role in the development of pathological processes like cancer, cardiovascular, and neurodegenerative disease. Therefore, it is crucial to have Genetics Toxicology tests that allow rapid and accurate identification of the mutagenic potential of a xenobiotic. Currently the most widely used technique is the “In vitro mammalian cell micronucleus test” performed by optical microscopy, but some problems have been highlighted, including the number of cells analyzed, the high subjectivity of the reading at the microscope and the long analysis times.

Aim

The aim of this work was to develop a study protocol, for the automation of the “In vitro mammalian cell micronucleus test”, by flow cytometry (FCM) analysis, to overcome the limits that afflict the optical microscopy.

Methods

The study was conducted on peripheral blood lymphocytes treated with three known clastogens and three known aneugens.

Results

The results obtained by the proposed FCM technique compared with those obtained through the validated method, demonstrated that the increase of micronuclei percentage is perfectly comparable between the two methods.

Conclusions

This fact, in view of results supported by a high number of cells analyzed and obtained by an accurate and objective reading, with a considerable reduction of the analysis time, can support a future request for validation of the micronucleus analysis by FCM. © 2017 International Clinical Cytometry Society
Socially Desirable Responding and College Students with Dyslexia: Implications for the Assessment of Anxiety and Depression
Authors: Nelson Jason M. , Liebel Spencer W.
Published: July 2017

We investigated self‐reported depressive and anxiety‐related symptoms among college students with dyslexia, with emphasis on the role of socially desirable responding (SDR) in understanding these reports. Analyses included examination of differences in self‐reported depressive symptoms, anxiety‐related symptoms, and SDR. We also examined the relationships among SDR, depressive symptoms, anxiety‐related symptoms, and reading skills. Participants with dyslexia demonstrated significantly higher SDR than did participants without dyslexia, and higher SDR was significantly associated with lower self‐reported depressive and anxiety‐related symptoms. Moreover, higher SDR was significantly associated with lower reading skills. There was no group difference on anxiety‐related symptoms, but participants with dyslexia had higher depressive symptoms than did participants without dyslexia when SDR was controlled. Implications for the assessment of anxiety and depression among college students with dyslexia are discussed. Copyright © 2017 John Wiley & Sons, Ltd.