bluuebunny/crossref_metadata_2025 huggingface dataset:
Features of vortex split MSSWs that are problematic to forecast
Authors: Taguchi Masakazu
Published: August 2016

A companion paper demonstrated that it is more difficult to forecast major stratospheric sudden warmings (MSSWs) of the vortex split type on medium range time scales of about 2 weeks than other MSSWs. As its extension, this study further investigates more specific features of planetary waves for the greater difficulty through a composite analysis using the Japanese 55‐year reanalysis data and the Japan Meteorological Agency 1‐month hindcast data. Results show that the hindcast data of about two week lead times to the MSSWs largely underestimate the vortex stretching and split at 10 hPa, and the forcing and propagation of planetary wave of zonal wavenumber 2 to the stratosphere. The underestimation in the wave forcing largely reflects a deficiency in simulating a nonlinear, or quadratic, term in wave anomalies (meridional wind and temperature) from the climatology.
Bauwerksprüfung unterstützt durch neuartige Besichtigungstechniken – Erste Erfahrungen
Authors: Holst Ralph , Sperber Martin , Gößmann Rainer
Published: August 2016

Die Straßenverkehrsinfrastruktur ist durch steigende Belastungen und zunehmende Durchschnittsalter mittlerweile vielfach am Rande der Leistungsfähigkeit angelangt. In Zukunft werden Baumaßnahmen in erheblichem Umfang durchzuführen sein. Damit diese Erhaltungsmaßnahmen technisch und wirtschaftlich optimal durchgeführt werden können, ist es notwendig, frühzeitig und umfassend über den aktuellen Zustand, vor allem der Brücken, informiert zu sein. Hierfür ist es notwendig, den Zustand dieser zu erfassen, neue innovative Techniken zur Unterstützung der Bauwerksprüfung nach DIN 1076 sollen hinsichtlich ihrer Eignung überprüft werden.

Unbemannte Fluggeräte bzw. UAS (Unmanned Aerial System) bieten vielfältige Möglichkeiten zur Bilderfassung und können als unterstützendes technisches Hilfsmittel bei der Bauwerksprüfung zum Einsatz kommen. Im Rahmen eines Forschungsprojekts wurden drei Brücken mithilfe von UAS beflogen, wodurch Schäden identifiziert werden konnten. Insbesondere die Möglichkeit zur Befliegung schwer zugänglicher Stellen, Zeitersparnis während einer Prüfung und die automatisierte Schadenserkennung machen diese Technologie für die Brückenprüfung interessant. Durch die gezielte Anwendung der UAS‐Technologie kann eine Reduzierung der Nutzungseinschränkung des Bauwerks verbunden mit einer Qualitätssteigerung der Ergebnisse erreicht werden.
Parsimonious mixtures of multivariate contaminated normal distributions
Authors: Punzo Antonio , McNicholas Paul D.
Published: August 2016

A mixture of multivariate contaminated normal distributions is developed for model‐based clustering. In addition to the parameters of the classical normal mixture, our contaminated mixture has, for each cluster, a parameter controlling the proportion of mild outliers and one specifying the degree of contamination. Crucially, these parameters do not have to be specifieda priori, adding a flexibility to our approach. Parsimony is introduced via eigen‐decomposition of the component covariance matrices, and sufficient conditions for the identifiability of all the members of the resulting family are provided. An expectation‐conditional maximization algorithm is outlined for parameter estimation and various implementation issues are discussed. Using a large‐scale simulation study, the behavior of the proposed approach is investigated and comparison with well‐established finite mixtures is provided. The performance of this novel family of models is also illustrated on artificial and real data.
Triboluminescence and crystal structure of the complex [Eu(NО3)3(HMPA)3]: role of cleavage planes
Authors: Bukvetskii B. V. , Mirochnik A. G. , Zhikhareva P. A.
Published: August 2016

The atomic structure of crystals of the [Eu(NО3)3(HMPA)3] [hexamethylphosphotriamide (HMPA)] complex characterized by an intensive luminescence and triboluminescence was determined using X‐ray structural analysis. Noncentrosymmetric crystals have a monoclinic syngony: a = 16.0686 (3), b = 11.0853 (2), c = 20.9655 Å (4), β = 93.232° (1), space group P21, Z = 4, ρcalc = 1.560 g/cm3. The crystal structure is represented by individual С18Н54EuN12O12P3 complexes linked through van der Waals interactions with clearly expressed cleavage planes. The Eu(III) atom coordination polyhedron reflected the state of a distorted square antiprism. Structural aspects of the suggested model, including formation of triboluminescence properties, were considered and the role of the cleavage planes was discussed.
Resonant and non‐resonant energy transfer from Ce3+ → X (X = Tb3+, Eu3+ or Dy3+) in NaMgSO4F material
Authors: Choubey S. R. , Gedam S. C. , Dhoble S. J.
Published: August 2016

An inorganic NaMgSO4F fluoride material was prepared by the wet chemical method and studied for its photoluminescence (PL) and resonant–non‐resonant energy transfer (RET and NORET) capabilities between Ce3+ → Tb3+, Ce3+ → Eu3+ and Ce3+ → Dy3+ rare earth ions. The Tb3+ emission for Ce3+ → Tb3+ transfers under ultraviolet (UV) wavelengths peaked at 491, 547, and 586 nm, for excitation at 308 nm due to 5D4 → 7FJ (J = 4, 5, 6) transitions. Eu emission spectra were observed at 440 nm (Eu2+), 593 nm and 616 nm (Eu3+) recorded for different concentrations of materials, whereas Dy3+ emission from Ce3+ → Dy3+ transfer under UV wavelengths peaked at 485 nm and 577 nm due to 4F9/2 → 6H15/2 and 6H13/2 transitions. The purpose of the present study is to understand the RET and NORET effects of Tb3+, Eu3+ and Dy3+ co‐doping in a NaMgSO4F:Ce3+ luminescent material, which could be used as a green‐emitting material for lamp phosphors.
Radical‐scavenging activity of penicillin G, ampicillin, oxacillin, and dicloxacillin
Authors: Berczyński Paweł , Kładna Aleksandra , Kruk Irena , Aboul‐Enein Hassan Y.
Published: August 2016

The aim of this study was to characterize the antioxidant activity of penicillin G (PG), ampicillin (AMP), oxacillin (OX) and dicloxacillin (DOX) through their reactivity towards reactive oxygen species (superoxide anion radical,
; hydroxyl radical, HO•; peroxyl radical, ROO•; hydrogen peroxide, H2O2; DPPH•) using various in vitro antioxidant assays with chemiluminescence (CL) and spectrophotometry as measurement techniques. In hydroxyl radical assays , PG, OX and AMP were found to inhibit the CL signal arising from the Fenton‐like reaction in a dose‐dependent manner with IC50 = 0.480 ± 0.020 mM, IC50 = 0.569 ± 0.021 mM, and IC50 = 0.630 ± 0.019 mM, respectively. The highest reactivity of PG among the tested penicillins towards the HO radical was confirmed in the deoxyribose degradation assay. In the ABAP‐derived ROO radical assay, the radical‐scavenging ability of the test penicillins was in the following order: AMP > PG > DOX > OX. The number of reduced DPPH radicals by the drugs tested was <1 being the biggest for PG. The weak antioxidant capacity of the test penicillins was confirmed in the trolox antioxidant capacity assay (0.075 ± 0.004; 0.093 ± 0.006; 0.123 ± 0.005; 0.126 ± 0.004) for OX, AMP, DOX, PG, respectively. Use of luminol as a CL probe for estimation of penicillin reactivity towards H2O2 showed that only AMP was able to quench light emission; the remaining antibiotics demonstrated a strong enhancing effect. All the examined compounds showed a weak antioxidant potential when estimated using the ferric‐ferrozine assay. This study is the first to report the evaluation of test penicillins as antioxidants under the same reaction conditions.
Supplementation with linoleic acid‐rich soybean oil stimulates macrophage foam cell formation via increased oxidative stress and diacylglycerol acyltransferase1‐mediated triglyceride biosynthesis
Authors: Rom Oren , Jeries Helana , Hayek Tony , Aviram Michael
Published: August 2016

During the last decades there has been a staggering rise in human consumption of soybean oil (SO) and its major polyunsaturated fatty acid linoleic acid (LA). The role of SO or LA in cardiovascular diseases is highly controversial, and their impact on macrophage foam cell formation, the hallmark of early atherogenesis, is unclear. To investigate the effects of high SO or LA intake on macrophage lipid metabolism and the related mechanisms of action, C57BL/6 mice were orally supplemented with increasing levels of SO‐based emulsion or equivalent levels of purified LA for 1 month, followed by analyses of lipid accumulation and peroxidation in aortas, serum and in peritoneal macrophages (MPM) of the mice. Lipid peroxidation and triglyceride mass in aortas from SO or LA supplemented mice were dose‐dependently and significantly increased. In MPM from SO or LA supplemented mice, lipid peroxides were significantly increased and a marked accumulation of cellular triglycerides was found in accordance with enhanced triglyceride biosynthesis rate and overexpression of diacylglycerol acyltransferase1 (DGAT1), the key enzyme in triglyceride biosynthesis. In cultured J774A.1 macrophages treated with SO or LA, triglyceride accumulated via increased oxidative stress and a p38 mitogen‐activated protein kinase (MAPK)‐mediated overexpression of DGAT1. Accordingly, anti‐oxidants (pomegranate polyphenols), inhibition of p38 MAPK (by SB202190) or DGAT1 (by oleanolic acid), all significantly attenuated SO or LA‐induced macrophage triglyceride accumulation. These findings reveal novel mechanisms by which supplementation with SO or LA stimulate macrophage foam cell formation, suggesting a pro‐atherogenic role for overconsumption of SO or LA. © 2016 BioFactors, 43(1):100–116, 2017
Systematic review of the methodological and reporting quality of case series in surgery
Authors: Agha R A , Fowler A J , Lee S-Y , Gundogan B , Whitehurst K , Sagoo H K , Jeong K J L , Altman D G , Orgill D P
Published: August 2016

Background

Case series are an important and common study type. No guideline exists for reporting case series and there is evidence of key data being missed from such reports. The first step in the process of developing a methodologically sound reporting guideline is a systematic review of literature relevant to the reporting deficiencies of case series.

Methods

A systematic review of methodological and reporting quality in surgical case series was performed. The electronic search strategy was developed by an information specialist and included MEDLINE, Embase, Cochrane Methods Register, Science Citation Index and Conference Proceedings Citation index, from the start of indexing to 5 November 2014. Independent screening, eligibility assessments and data extraction were performed. Included articles were then analysed for five areas of deficiency: failure to use standardized definitions, missing or selective data (including the omission of whole cases or important variables), transparency or incomplete reporting, whether alternative study designs were considered, and other issues.

Results

Database searching identified 2205 records. Through the process of screening and eligibility assessments, 92 articles met inclusion criteria. Frequencies of methodological and reporting issues identified were: failure to use standardized definitions (57 per cent), missing or selective data (66 per cent), transparency or incomplete reporting (70 per cent), whether alternative study designs were considered (11 per cent) and other issues (52 per cent).

Conclusion

The methodological and reporting quality of surgical case series needs improvement. The data indicate that evidence-based guidelines for the conduct and reporting of case series may be useful.
Genetic and environmental components of female depression as a function of the severity of the disorder
Authors: Rusby James S. M. , Tasker Fiona , Cherkas Lynn
Published: August 2016

Background

Both clinical care and genome‐wide studies need to account for levels of severity in the etiology of depression. The purpose of the study is to estimate the genetic and environmental components of female depression as a function of the severity of the disorder.

Methods

A genetic and environmental model analysis of depression incidence was made using the IOP Depression Severity Measure (IDSM). Details of lifetime depression incidence were obtained by questionnaire from twins on the DTR registry. Data from 1449 matched female twin pairs in the age range 19–85 years in four ordinal categories of increasing severity were employed in the analysis.

Results

Estimates of additive and dominance genetic components of 27% and 25% were found when all three levels of depression were included, and near zero and 33% when the recurrent/severe level was excluded. Shared environmental effects were not significant in either case, but the estimate for random environmental effects was greater when the severe level was excluded.

Conclusions

These results suggest that the incidence of severe depression is associated with homozygotic alleles and the less severe with heterozygotic alleles. This is in accord with the finding that the hereditary component of severe depression is relatively high and that milder forms are more dependent on life‐time environmental factors. Such conclusions have clinical implications for the diagnosis and treatment of the disorder by practicing psychiatrists. They also lead to the importance of focusing future genome‐wide and linkage studies on those females with severe levels of depression if progress in identifying genetic risk loci is to be made.
Long‐term prognostic value of risk scores after drug‐eluting stent implantation for unprotected left main coronary artery: A pooled analysis of the ISAR‐LEFT‐MAIN and ISAR‐LEFT‐MAIN 2 randomized clinical trials
Authors: Xhepa Erion , Tada Tomohisa , Kufner Sebastian , Ndrepepa Gjin , Byrne Robert A. , Kreutzer Johanna , Ibrahim Tareq , Tiroch Klaus , Valgimigli Marco , Tölg Ralf , Cassese Salvatore , Fusaro Massimiliano , Schunkert Heribert , Laugwitz Karl L. , Mehilli Julinda , Kastrati Adnan
Published: August 2016

Objectives

To evaluate the long‐term prognostic value of risk scores in the setting of drug‐eluting stent (DES) implantation for uLMCA.

Background

Data on the prognostic value of novel risk scores developed to select the most appropriate revascularization strategy in patients undergoing DES implantation for uLMCA disease are relatively limited.

Methods

The study represents a patient‐level pooled analysis of the ISAR‐LEFT‐MAIN (607 patients randomized to paclitaxel‐eluting or sirolimus‐eluting stents) and the ISAR‐LEFT‐MAIN‐2 (650 patients randomized to everolimus‐eluting or zotarolimus‐eluting stents) randomized trials. The Syntax Score (SxScore) as well the Syntax Score II (SS‐II), the EuroSCORE and the Global Risk Classification (GRC) were calculated. The primary outcome was all‐cause mortality.

Results

At a mean follow‐up of 3 years there were 160 deaths (12.7%). The death‐incidence was significantly higher in the upper tertiles than in the intermediate or lower ones for all risk scores (log‐rank test P < 0.01 for all comparisons). The discriminatory power of a multivariable model for prediction of 3‐year mortality was significantly improved after the inclusion of EuroSCORE (adjusted area under the receiver operating characteristic (ROC) curve = 0.779, 95% confidence interval 0.747 to 0.810, P = 0.008), but not after the inclusion of SxScore, SS II, or GRC.

Conclusions

In patients undergoing DES implantation for uLMCA disease, all evaluated risk scores were able to stratify the mortality risk at long‐term follow‐up. EuroSCORE was the only risk score that significantly improved the discriminatory power of a multivariable model to predict long‐term mortality. © 2016 Wiley Periodicals, Inc.
Rapid pacing using the left ventricular guidewire: Reviving an old technique to simplify BAV and TAVI procedures
Authors: Faurie Benjamin , Abdellaoui Mohamed , Wautot Fabrice , Staat Patrick , Champagnac Didier , Wintzer‐Wehekind Jérome , Vanzetto Gérald , Bertrand Bernard , Monségu Jacques
Published: August 2016

Objectives

We sought to demonstrate the safety and efficacy of rapid left ventricular (LV) pacing through the guidewire during balloon aortic valvuloplasty (BAV) and Transaortic valve implantation (TAVI).

Background

Right ventricular temporary pacing during TAVI and BAV is time‐consuming and associated with vascular and pericardial complications.

Methods

Rapid left ventricular pacing was provided via the back‐up 0.035″ guidewire. The cathode of an external pacemaker was placed on the tip of the 0.035″ wire and the anode on a needle inserted into the groin. Insulation was ensured by the balloon or TAVI catheter.

Results

38 BAV and 87 TAVI procedures were performed in 113 consecutive patients in three centers with one for one pacing (160–200 bpm) in all patients. A significant reduction in blood pressure was achieved with a mean systolic pressure of 44 mm Hg during stimulation. Mean procedural time was 49.7 ± 31 min for BAV and 68.7 ± 30.9 for TAVI. A temporary venous pacemaker was required in 12 patients; only 12% of TAVI patients had a femoral central venous catheter. Femoral venous puncture was not performed in BAV patients. No venous vascular complications were observed. One case of successfully treated tamponade (0.8%) occurred 8 hr post procedure. In‐hospital mortality rates were 4.6% and 2.6% in the TAVI and BAV groups, respectively.

Conclusions

Use of the LV guidewire for rapid pacing during BAV and TAVI was shown to be simple, reproducible, and prevented complications associated with RV temporary leads thus potentially simplifying TAVI and enhancing its safety. © 2016 Wiley Periodicals, Inc.
Comparison of a vascular closure device versus the radial approach to reduce access site complications in non‐ST‐segment elevation acute coronary syndrome patients: The angio‐seal versus the radial approach in acute coronary syndrome trial
Authors: Andrade Pedro B. , Mattos Luiz A. , Rinaldi Fábio S. , Bienert Igor C. , Barbosa Robson A. , Labrunie André , Tebet Marden , Esteves Vinícius , Abizaid Alexandre , Sousa Amanda R.
Published: August 2016

Objectives

To compare the radial versus femoral approach using Angio‐Seal for the incidence of access site complications among non‐ST‐segment elevation acute coronary syndrome patients undergoing invasive strategy.

Background

Arterial access is a major site of complications after invasive coronary procedures. Vascular closure devices provide more comfort to patients decreasing time to hemostasis and need for bed rest. However, the inconsistency of data proving their safety limits their routine adoption as a strategy to prevent vascular complications.

Methods

Single‐center non‐inferiority trial where 240 patients were randomized to radial or femoral access using Angio‐Seal. The primary objective was the occurrence of complications at the arterial puncture site until 30 days after the procedure.

Results

There were no baseline clinical differences between groups, except for a greater prevalence of female patients in the radial group (33.3 vs. 20.0%, P = 0.020). Hemostasis was achieved in the entire radial group with the use of TR Band and in 95% of the procedures in the femoral group with Angio‐Seal (P = 0.029). Except for a higher incidence of asymptomatic arterial occlusion in the radial group, there were no differences among the other analyzed outcomes. According to the noninferiority test, the use of Angio‐Seal was noninferior to the radial approach, considering the margin of 15% (12.5 vs. 13.3%, difference −0.83%, 95% CI −9.31 − 7.65, P for noninferiority <0.001).

Conclusions

Angio‐Seal seems noninferior in the incidence of access site complications at 30 days when compared with the radial approach. © 2016 Wiley Periodicals, Inc.
Influence of a Combination of Flocculants on Harvesting of Chaetoceros gracilis Marine Microalgae
Authors: Pérez Leticia , Salgueiro Jose Luis , Maceiras Rocío , Cancela Ángeles , Sánchez Ángel
Published: August 2016

Harvesting is one of the most important operations in microalgal biomass utilization. Two types of flocculants are widely used in flocculation. Inorganic flocculants are usually cheaper than organic flocculants, but leave more contaminants on the culture media. The combination of one inorganic and one organic flocculant and its synergy for the marine microalgae Chaetoceros gracilis harvesting process is reported. The efficiency of eight inorganic and five organic flocculants was studied. The results show that, when only FeCl3 was used, high doses were required for high levels of biomass recovery, whereas chitosan alone led to poor recoveries. However, when both flocculants were used in combined flocculation, total biomass recovery was achieved, even at low doses.
Amplified Charge Transfer for Anionic Redox Probes through Oriented Mesoporous Silica Thin Films
Authors: Karman Cheryl , Vilà Neus , Walcarius Alain
Published: August 2016

Diffusion of anionic species through ordered mesoporous silica films is considerably restricted due to electrostatic repulsion by the negatively charged silica surface and this effect is even worse in low ionic strength media (owing to Donnan exclusion effects). This is at the origin of the poor electrochemical response of anionic redox probes at electrodes modified with such mesoporous thin films. Here, by using indium–tin oxide (ITO) electrodes covered with vertically aligned mesoporous silica films generated by electrochemically assisted self‐assembly (EASA), we show that charge transfer for anionic redox probes [i.e. Fe(CN)63−/4−] can be dramatically amplified by using a neutral [ferrocene dimethanol, Fc(MeOH)2] or cationic [(Ru(NH3)63+] redox mediator. This has been observed by cyclic voltammetry, showing current enhancement in the presence of the mediator, which acts as a mobile electron shuttle between the charge‐excluded Fe(CN)63−/4− species from the mesoporous silica film and the underlying ITO surface owing to the ability of the mediator species to diffuse freely through the oriented mesopore channels. This behavior was significantly affected by the relative contents of Fe(CN)63−/4− probe to Fc(MeOH)2 mediator, the potential scan rate, and the supporting electrolyte concentration. The most effective improvements were reached at low Fe(CN)63−/4− concentration, high mediator content, low potential scan rate, and low ionic strength.
Supramolecular Interactions Direct the Formation of Two Structural Polymorphs from One Building Unit in a One‐Pot Synthesis
Authors: Zhang Ming‐Yuan , Wang Zhenxing , Yang Tao , Zhang Yuexing , Ma Xiong‐Feng , Sun Yi‐Chen , Ouyang Zhong‐Wen , Kurmoo Mohamedally , Zeng Ming‐Hua
Published: August 2016

Two polymorphs of supramolecular isomers, a discrete dimer and a zig‐zag chain, having the same chemical composition, [Mn(Hbit)Cl2] (Hbit=1‐methyl‐2‐(1H‐1,2,3‐triazol‐4‐yl)‐1H‐benzo[d]imidazole), were obtained solvothermally in a one‐pot synthesis. The isomers differ in a number of ways: orange blocks versus pale‐yellow needles, triclinic P
versus orthorhombic Pbcn, double μ2‐Cl versus alternate single and triple μ2‐Cl, coordination number 5 versus 6, and antiparallel versus parallel near‐neighbor orientation of Hbit. The packing in each case is driven by the supramolecular interactions, H‐bonds (N−H⋅⋅⋅Cl, C−H⋅⋅⋅Cl) and π⋅⋅⋅π overlaps, calculated to be in the range 20–36 kcal mol−1. Calculations gave a difference of only 2 kcal mol−1 in favor of the dimer, which confirms with the observation of principally the dimer at short reaction time. ESI‐MS spectra of the dissolved crystals reveal the same fragments with similar distributions. The presence of two fragments at m/z 286.96 [MnIV(Hbit)Cl‐2H]+ and 323.94 [MnIII(Hbit)Cl2]+ indicates that [Mn(Hbit)Cl2] is the building unit in both cases; thus, the different orientations of the ligands lead to the two polymorphs stabilized by the respective supramolecular interactions. Importantly, the chain form represents the first example with alternate single and triple μ2‐Cl bridges. The magnetic interactions are weakly antiferromagnetic in both cases, with J in the range 0.07–0.34 cm−1; however, high‐field EPR analysis reveals moderate magneto‐anisotropy with D=0.26(1) cm−1, E=0.06(1) cm−1 and D=0.17(1) cm−1, E=0.03(1) cm−1, respectively.
En Route to Stimuli‐Responsive Boron‐, Nitrogen‐, and Sulfur‐Doped Polycyclic Aromatic Hydrocarbons
Authors: Hertz Valentin M. , Massoth Julian G. , Bolte Michael , Lerner Hans‐Wolfram , Wagner Matthias
Published: August 2016

Replacing both meso carbon atoms of the polycyclic aromatic hydrocarbon (PAH) bisanthene by boron atoms creates an efficient blue fluorophore with a strong electron‐accepting character. The corresponding meso‐B,S‐doped bisanthene exhibits a solvent‐dependent green‐to‐orange photoluminescence and undergoes a reversible reduction at E
=−2.06 V (vs. FcH/FcH+). After oxidation of the sulfur atom, the resulting sulfoxide emits in the blue range of the spectrum, shows only negligible solvatochromism, and a reversible redox transition at E
=−1.74 V. Several related B, N‐ and B, S‐containing PAHs have been prepared following the same modular synthetic procedure and are also described herein. In order to systematically compare their optoelectronic properties, all products have been investigated by cyclic voltammetry as well as UV/Vis absorption/emission spectroscopy.
Efficient Enzymatic Preparation of 13N‐Labelled Amino Acids: Towards Multipurpose Synthetic Systems
Authors: da Silva Eunice S. , Gómez‐Vallejo Vanessa , Baz Zuriñe , Llop Jordi , López‐Gallego Fernando
Published: August 2016

Nitrogen‐13 can be efficiently produced in biomedical cyclotrons in different chemical forms, and its stable isotopes are present in the majority of biologically active molecules. Hence, it may constitute a convenient alternative to Fluorine‐18 and Carbon‐11 for the preparation of positron‐emitter‐labelled radiotracers; however, its short half‐life demands for the development of simple, fast, and efficient synthetic processes. Herein, we report the one‐pot, enzymatic and non‐carrier‐added synthesis of the 13N‐labelled amino acids l‐[13N]alanine, [13N]glycine, and l‐[13N]serine by using l‐alanine dehydrogenase from Bacillus subtilis, an enzyme that catalyses the reductive amination of α‐keto acids by using nicotinamide adenine dinucleotide (NADH) as the redox cofactor and ammonia as the amine source. The integration of both l‐alanine dehydrogenase and formate dehydrogenase from Candida boidinii in the same reaction vessel to facilitate the in situ regeneration of NADH during the radiochemical synthesis of the amino acids allowed a 50‐fold decrease in the concentration of the cofactor without compromising reaction yields. After optimization of the experimental conditions, radiochemical yields were sufficient to carry out in vivo imaging studies in small rodents.
Probing Metal Ion Complexation of Ligands with Multiple Metal Binding Sites: The Case of Spiropyrans
Authors: Baldrighi Michele , Locatelli Giulia , Desper John , Aakeröy Christer B. , Giordani Silvia
Published: August 2016

Among known molecular switches, spiropyrans attract considerable interest because of their reversible responsiveness to external stimuli and the deep conformational and electronic changes that characterize the switching process between the two isomeric forms [spiropyran (SP) and merocyanine (MC)]. Metal coordination is one of the most interesting aspects of spiropyrans for its potential in sensing, catalysis, and medicinal chemistry, but little is known about the details surrounding spiropyran–metal ion binding. We investigated the interplay between an N‐modified 8‐methoxy‐6‐nitrospiropyran (SP‐E), designed to provide appropriate molecular flexibility and a range of competing/collaborative metal binding sites, with Mg2+, Cu2+ and Zn2+, which were chosen for their similar coordination geometry preferences while differing in their hard/soft character. The formed molecular complexes were studied by means of UV/Vis, fluorescence, and NMR spectroscopies and mass spectrometry, and the crystal structure of the SP‐E–Cu complex was also obtained. The results indicate that the Mg2+, Zn2+ and Cu2+ complexes have identical coordination stoichiometry. Furthermore, the Mg2+ and Zn2+ complexes display fluorescence properties in solution and visible‐light responsiveness. These results provide important spectroscopic and structural information that can serve as a foundation for rational design of spiropyran‐based smart materials for metal sensing and scavenging applications.
Influence of Polymer Electronics on Selective Dispersion of Single‐Walled Carbon Nanotubes
Authors: Fong Darryl , Bodnaryk William J. , Rice Nicole A. , Saem Sokunthearath , Moran‐Mirabal Jose M. , Adronov Alex
Published: August 2016

The separation and isolation of semiconducting and metallic single‐walled carbon nanotubes (SWNTs) on a large scale remains a barrier to many commercial applications. Selective extraction of semiconducting SWNTs by wrapping and dispersion with conjugated polymers has been demonstrated to be effective, but the structural parameters of conjugated polymers that dictate selectivity are poorly understood. Here, we report nanotube dispersions with a poly(fluorene‐co‐pyridine) copolymer and its cationic methylated derivative, and show that electron‐deficient conjugated π‐systems bias the dispersion selectivity toward metallic SWNTs. Differentiation of semiconducting and metallic SWNT populations was carried out by a combination of UV/Vis‐NIR absorption spectroscopy, Raman spectroscopy, fluorescence spectroscopy, and electrical conductivity measurements. These results provide new insight into the rational design of conjugated polymers for the selective dispersion of metallic SWNTs.
Cubic Siloxanes with Both Si−H and Si−OtBu Groups for Site‐Selective Siloxane Bond Formation
Authors: Saito Shohei , Yamasue Nao , Wada Hiroaki , Shimojima Atsushi , Kuroda Kazuyuki
Published: August 2016

Invited for the cover of this issue is the group of Atsushi Shimojima and Kazuyuki Kuroda at Waseda University. The image depicts the structure of cage‐type octasiloxane, the smallest “glass” cube in the universe, and its selective functionalization. Read the full text of the article at 10.1002/chem.201601906.
ChemInform Abstract: Donharrisite, Ni3HgS3: Crystal Structure and Revision of the Chemical Formula.
Authors: Bindi Luca , Paar Werner H.
Published: August 2016

The title mineral crystallizes in the monoclinic space group C2/m with Z = 4 (single crystal XRD).
ChemInform Abstract: LiNa5Mo9O30: Crystal Growth, Linear, and Nonlinear Optical Properties.
Authors: Zhang Weiguo , Yu Hongwei , Cantwell Jacqueline , Wu Hongping , Poeppelmeier Kenneth R. , Halasyamani P. Shiv
Published: August 2016

Polycrystalline LiNa5Mo9O30 is prepared by firing stoichiometric amounts of Na2CO3, Li2MoO4, and MoO3 in air (Pt crucible, 1.
ChemInform Abstract: The First Urea‐Based Ionic Liquid‐Stabilized Magnetic Nanoparticles: An Efficient Catalyst for the Synthesis of Bis(indolyl)methanes and Pyrano[2,3‐d]pyrimidinone Derivatives.
Authors: Zolfigol Mohammad Ali , Ayazi‐Nasrabadi Roya , Baghery Saeed
Published: August 2016

Simple solvent free procedures using the title catalyst are presented for the condensation reaction of aromatic aldehydes with 2‐methylindole and for the one‐pot three component reaction of aldehydes, barbituric acid and malononitrile to give the title products in high yields.
ChemInform Abstract: Generation of N‐Aminosulfonamides via a Photo‐Induced Fixation of Sulfur Dioxide into Aryl/Alkyl Halides.
Authors: Li Yuewen , Zheng Danqing , Li Zhenhua , Wu Jie
Published: August 2016

A novel catalyst‐free aminosulfonylation through insertion of sulfur dioxide with aryl/alkyl halides enabled by photoenergy is presented.
ChemInform Abstract: Tin Tetrachloride Pentahydrate‐Catalyzed Regioselective Chlorohydroxylation of α,β‐Unsaturated Ketones in Water with Selectfluor as a Chlorine Source.
Authors: Liang Deqiang , Li Xiangguang , Lan Qing , Huang Wenzhong , Yuan Lin , Ma Yinhai
Published: August 2016

Aroyl groups in substrates (I) are essential for the chlorohydroxylation reaction.
ChemInform Abstract: Cu‐Catalyzed Multicomponent Reaction of Styrenes, Perfluoroalkyl Halide, Alcohol, and tert‐Butyl Hydroperoxide: One‐Pot Synthesis of (Z)‐β‐Alkoxyperfluoroalkenone.
Authors: Luo Qiang , Liu Chunmei , Tong Jingjing , Shao Ying , Shan Wenyu , Wang Hanghang , Zheng Hao , Cheng Jiang , Wan Xiaobing
Published: August 2016

The chemo‐ and stereoselective title reaction proceeds under mild conditions and has a broad substrate scope.
ChemInform Abstract: A Facile One‐Pot Domino Reaction for the Stereoselective Synthesis of Acryl Derivatives Promoted by Ca(OTf)2.
Authors: Yaragorla Srinivasarao , Saini Pyare Lal , Pareek Abhishek , Almansour Abdulrahman I. , Arumugam Natarajan
Published: August 2016

Facile multicomponent reactions for the synthesis of indolyl and oxindolyl acrylates as well as bisacrylates are presented.
ChemInform Abstract: Stereoselective Synthesis of Tetrahydroindolizines Through the Catalytic Formation of Pyridinium Ylides from Diazo Compounds.
Authors: Day Jonathan , McKeever‐Abbas Ben , Dowden James
Published: August 2016

Iron(III) and copper(I) complexes catalyze multicomponent cycloaddition reactions between diazo compounds, pyridines, and electrophilic alkenes to provide alkaloid‐inspired tetrahydroindolizidines in a diastereoselective manner.
ChemInform Abstract: Copper‐Catalyzed S—C/S—N Bond Interconversions.
Authors: Wen Jian , Cheng Hanchao , Dong Shunxi , Bolm Carsten
Published: August 2016

Under an atmosphere of dioxygen, copper‐catalyzed de‐alkylation/amination sequences provide sulfonimidamides from unprotected sulfoximines in moderate to good yields.
ChemInform Abstract: PCl3‐Mediated Synthesis of Green/cyan Fluorescent Protein Chromophores Using Amino Acids.
Authors: Singh Thokchom Prasanta , Shunmugam Raja
Published: August 2016

A convenient and rapid synthesis of green fluorescent protein (FP) chromophores (IV) and cyan FP chromophores (VI) starting from commercially available aromatic amino acids, acetyl chlorides, and anilines is described.
ChemInform Abstract: Guanidine Hydrochloride: A Highly Efficient Organocatalyst for the Synthesis of 12‐Aryl‐8,9,10,12‐tetrahydrobenzo[a]xanthene‐11‐ones under Solvent‐Free Conditions.
Authors: Sadeghpour Mahdieh , Olyaei Abolfazl , Rezaei Mortaza
Published: August 2016

The title xanthenes are efficiently prepared by condensation reactions of naphthols, various aromatic benzaldehydes, and dimedone under green reaction conditions.
ChemInform Abstract: Diversely Substituted Quinolines via Rhodium‐Catalyzed Alkyne Hydroacylation.
Authors: Neuhaus James D. , Morrow Sarah M. , Brunavs Michael , Willis Michael C.
Published: August 2016

The Rhodium‐catalyzed reaction of 2‐alkynyl anilines with aryl, hetaryl or alkyl aldehydes leads to 2‐aminophenyl enones which are further transformed into substituted quinolines endowed with diverse functional groups.
ChemInform Abstract: Tandem One Pot and Efficient Method for the Palladium‐Reagent‐Catalyzed Cross‐Coupling of Quinazoline Thiols.
Authors: Karuna P. Satya , Murthy R. V. V. Ramana , Reddy M. R. P. , Katari Naresh Kumar , Srinivas Kummari
Published: August 2016

Quinazoline sulfides are prepared by cross‐coupling of quinazoline thiols with alkyl and aryl bromides.
ChemInform Abstract: Organocatalytic Enantioselective Synthesis of P‐Stereogenic Chiral Oxazaphospholidines.
Authors: Wang Lanlan , Du Zhijun , Wu Qiang , Jin Rizhe , Bian Zheng , Kang Chuanqing , Guo Haiquan , Ma Xiaoye , Gao Lianxun
Published: August 2016

The desired phosphorus heterocycles are generally available with moderate enantioselectivity in the presence of triethylamine or 2‐methylimidazole and the organocatalyst TIA.
ChemInform Abstract: Convenient Synthesis of Phosphonohydrazines from Arylamines.
Authors: Kent Greggory T. , Blackburn Daniel J. , Gonzalez Joseph R. , Mayer Megan L. , Wu Weiming
Published: August 2016

Phosphonohydrazines are prepared from arylamines through diazotation with isoamyl nitrite and treatment with phosphite (II) in a one pot manner.
ChemInform Abstract: Truncaquinones A and B, Asterriquinones from Annulohypoxylon truncatum.
Authors: Surup Frank , Wiebach Vincent , Kuhnert Eric , Stadler Marc
Published: August 2016

isolation, structural elucidation and biological activity
ChemInform Abstract: Stereodivergent and Protecting‐Group‐Free Synthesis of the Helicascolide Family: A Rhodium‐Catalyzed Atom‐Economical Lactonization Strategy.
Authors: Haydl Alexander M. , Berthold Dino , Spreider Pierre A. , Breit Bernhard
Published: August 2016

Stereodivergent, robust, and concise total syntheses of all three representatives of the helicascolide family are achieved.
ChemInform Abstract: Highly Diastereoselective 1,6‐Conjugate Addition of Arylboronic Acids to Securinine.
Authors: Perez Marc , Ayad Tahar , Maillos Philippe , Poughon Valerie , Fahy Jacques , Ratovelomanana‐Vidal Virginie
Published: August 2016

Rhodium catalysis provides access to the single diastereomers of the regioselective C15‐arylation products of securinine in good yields.
ChemInform Abstract: Amine Synthesis via Transition Metal Homogeneous Catalyzed Hydrosilylation
Authors: Li Bin , Sortais Jean‐Baptiste , Darcel Christophe
Published: August 2016

Review: [140 refs.
ChemInform Abstract: Rh‐Catalyzed Asymmetric 1,4‐Addition Reactions to α,β‐Unsaturated Carbonyl and Related Compounds: An Update
Authors: Heravi Majid M. , Dehghani Mahzad , Zadsirjan Vahideh
Published: August 2016

Review: [356 refs.
ChemInform Abstract: Isocyanide and Meldrum′s Acid‐Based Multicomponent Reactions in Diversity‐Oriented Synthesis: From a Serendipitous Discovery Towards Valuable Synthetic Approaches
Authors: Shaabani Ahmad , Hooshmand Seyyed Emad
Published: August 2016

Review: 102 refs.
ChemInform Abstract: Tandem Bond‐Forming Reactions of 1‐Alkynyl Ethers
Authors: Minehan Thomas G.
Published: August 2016

Review: 54 refs.
ChemInform Abstract: Recent Advances in C—H Bond Aminations Catalyzed by Ruthenium Porphyrin Complexes
Authors: Intrieri Daniela , Carminati Daniela Maria , Gallo Emma
Published: August 2016

Review: 71 refs.
Economic independence in survivors of cancer diagnosed at a young age: A Norwegian national cohort study
Authors: Gunnes Maria W. , Lie Rolv Terje , Bjørge Tone , Syse Astri , Ruud Ellen , Wesenberg Finn , Moster Dag
Published: August 2016

BACKGROUND

The impact of cancer on socioeconomic outcomes is attracting attention as the number of survivors of cancer in young age continues to rise. This study examines economic independence in a national cohort of survivors of cancer at a young age in Norway.

METHODS

Through the linkage of several national registries, the study cohort comprised 1,212,013 individuals born in Norway during 1965 through 1985, of which 5440 had received a cancer diagnosis before age 25 years. Follow‐up was through 2007, and the main outcomes were receipt of governmental financial assistance, employment, income, and occupation. Analytic methods included Cox proportional hazard regression, log‐binomial regression, and quantile regression models.

RESULTS

Individuals in the cancer survivor group had an increased probability of receiving governmental financial assistance (men: hazard ratio [HR], 1.4; 95% confidence interval [CI], 1.3‐1.5; women: HR, 1.5; 95% CI, 1.3‐1.6) and of not being employed (men: HR, 1.4; 95% CI, 1.2‐1.7; women: HR, 1.4; 95% CI, 1.2‐1.6) compared with those in the noncancer group. Income discrepancies were particularly pronounced for survivors of central nervous system tumors. There was no difference in representation in higher skilled occupations.

CONCLUSIONS

Survivors of cancer at a young age in Norway had an increased risk of being economically dependent and unemployed. This was evident in several tumor groups and was most pronounced in female survivors. There were only small differences in income or representation in higher skilled occupations for most employed survivors compared with the noncancer group. The current results are important for understanding the impact of a cancer diagnosis at a young age on subsequent job market outcomes. Cancer 2016;122:3873–3882. © 2016 The Authors. Cancer published by Wiley Periodicals, Inc. on behalf of American Cancer Society.
Characterization of the Filum terminale as a neural progenitor cell niche in both rats and humans
Authors: Chrenek Ryan , Magnotti Laura M. , Herrera Gabriella R. , Jha Ruchira M. , Cardozo David L.
Published: August 2016

Neural stem cells (NSCs) reside in a unique microenvironment within the central nervous system (CNS) called the NSC niche. Although they are relatively rare, niches have been previously characterized in both the brain and spinal cord of adult animals. Recently, another potential NSC niche has been identified in the filum terminale (FT), which is a thin band of tissue at the caudal end of the spinal cord. While previous studies have demonstrated that NSCs can be isolated from the FT, the in vivo architecture of this tissue and its relation to other NSC niches in the CNS has not yet been established. In this article we report a histological analysis of the FT NSC niche in postnatal rats and humans. Immunohistochemical characterization reveals that the FT is mitotically active and its cells express similar markers to those in other CNS niches. In addition, the organization of the FT most closely resembles that of the adult spinal cord niche. J. Comp. Neurol. 525:661–675, 2017. © 2016 Wiley Periodicals, Inc.
The Structure and Torsional Dynamics of Two Methyl Groups in 2‐Acetyl‐5‐methylfuran as Observed by Microwave Spectroscopy
Authors: Van Vinh , Stahl Wolfgang , Nguyen Ha Vinh Lam
Published: August 2016

The molecular‐beam Fourier transform microwave spectrum of 2‐acetyl‐5‐methylfuran is recorded in the frequency range 2–26.5 GHz. Quantum chemical calculations calculate two conformers with trans or cis configuration of the acetyl group, both of which are assigned in the experimental spectrum. All rotational transitions split into quintets due to the internal rotations of two nonequivalent methyl groups. By using the program XIAM, the experimental spectra can be simulated with standard deviations within the measurement accuracy, and yield well‐determined rotational and internal rotation parameters, inter alia the V3 potentials. Whereas the V3 barrier height of the ring‐methyl rotor does not change for the two conformers, that of the acetyl‐methyl rotor differs by about 100 cm−1. The predicted values from quantum chemistry are only on the correct order of magnitude.
An Azulene‐Fused Tetracene Diimide with a Small HOMO–LUMO Gap
Authors: Koide Taro , Takesue Moritaka , Murafuji Toshihiro , Satomi Koichiro , Suzuki Yasutaka , Kawamata Jun , Terai Kengo , Suzuki Mitsuharu , Yamada Hiroko , Shiota Yoshihito , Yoshizawa Kazunari , Tani Fumito
Published: August 2016

A newly prepared tetraazulene‐fused tetracene diimide (TA‐fused TDI) showed absorption in the near‐IR region owing to the effective extension of the π‐conjugated system as well as a large two‐photon absorption cross‐section (σ(2)=2140 GM) at 950 nm. Four reversible reduction processes and n‐type semiconductivity were also confirmed as attractive electronic properties of this compound.
Immunotherapy to Treat Cancer
Authors: McCune JS
Published: August 2016

This issue of Clinical Pharmacology & Therapeutics focuses on immunotherapy as an approach to treat cancer by generating or augmenting an immune response against it. The enthusiasm for immunotherapy has waxed and waned over the past century. Enthusiasm for immunotherapy has risen over the past decade due, in part, to data showing that cancer immunotherapy consistently improves overall survival in select patients with advanced‐stage cancer. Antitumor immunotherapy has broad potential and could be used to treat many different types of advanced‐stage cancer due to the durable and robust response that it elicits across a diverse spectrum of cancers. This issue covers various aspects of relevant therapeutic topics ranging from discovery of chimeric antigen receptor (CAR) T cells, development of novel immunotherapies using novel pharmacokinetic/dynamic modeling tools, to the utilization of immune checkpoint therapy. Regarding utilization, this issue addresses biomarker selection strategies for personalized treatment of non‐small cell lung cancer (NSCLC) with immune checkpoint therapy and also the management of the unique immune response adverse events (irAEs).
Is Ammonium Peroxydisulfate Indispensable for Preparation of Aniline‐Derived Iron–Nitrogen–Carbon Electrocatalysts?
Authors: Xie Nan‐Hong , Yan Xiang‐Hui , Xu Bo‐Qing
Published: August 2016

Iron and nitrogen co‐doped carbon (Fe‐N‐C) materials are among the most active non‐precious metal catalysts that could replace Pt‐based electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells and metal–air batteries. The synthesis of the Fe‐N‐C catalysts often involves the use of aniline as the precursor for both N and C and ammonium peroxydisulfate (APS) as an indispensable oxidative initiator for aniline polymerization. Herein, a detailed structure and catalytic ORR performance comparison of aniline‐derived Fe‐N‐C catalysts synthesized with and without the use of APS is reported. The APS‐free preparation, which uses FeIII ions as the Fe source as well as the aniline polymerization initiator, results in a cleaner and simpler Fe‐N‐C catalyst with a higher activity for the ORR. We show that APS is not necessary for the preparation and even detrimental to the performance of the catalyst.
Tree seedling richness, but not neighborhood composition, influences insect herbivory in a temperate deciduous forest community
Authors: Murphy Stephen J. , Xu Kaiyang , Comita Liza S.
Published: August 2016

Insect herbivores can serve as important regulators of plant dynamics, but their impacts in temperate forest understories have received minimal attention at local scales. Here, we test several related hypotheses about the influence of plant neighborhood composition on insect leaf damage in southwestern Pennsylvania, USA. Using data on seedlings and adult trees sampled at 36 sites over an approximately 900 ha area, we tested for the effects of total plant density, rarefied species richness (i.e., resource concentration and dietary‐mixing hypotheses), conspecific density (i.e., Janzen–Connell hypothesis), and heterospecific density (i.e., herd‐immunity hypothesis), on the proportion of leaf tissue removed from 290 seedlings of 20 species. We also tested for the effects of generic‐ and familial‐level neighborhoods. Our results showed that the proportion of leaf tissue removed ranged from zero to just under 50% across individuals, but was generally quite low (<2%). Using linear mixed models, we found a significant negative relationship between insect damage and rarefied species richness, but no relationship with neighborhood density or composition. In addition, leaf damage had no significant effect on subsequent seedling growth or survival, likely due to the low levels of damage experienced by most individuals. Our results provide some support for the resource concentration hypothesis, but suggest a limited role for insect herbivores in driving local‐scale seedling dynamics in temperate forest understories.
Characteristics of Pulsed Heavy Ion Beam Generated in Bipolar Pulse Accelerator
Authors: ITO HIROAKI , KITAJIMA KAZUKI
Published: August 2016

We have developed a new type of a pulsed ion beam accelerator named “bipolar pulse accelerator” for improvement of the purity of the intense pulsed ion beam. The system utilizes a magnetically insulated accelerate on gap and was operated with the bipolar pulse. A coaxial gas puff plasma gun was used as an ion source, which was placed inside of the grounded anode. Source plasma (nitrogen) of current density of ≈30 A/cm2 and pulse duration of ≈1.0 μs was injected into the acceleration gap. When the bipolar pulse of −114 kV, 70 ns (first pulse) and 85 kV, 62 ns (second pulse) was applied to the drift tube, the ions were successfully accelerated from the grounded anode to the drift tube in the first gap by the negative pulse of the bipolar pulse. The pulsed ion beam with current density of 60 A/cm2 and pulse duration of ≈50 ns was obtained at 48 mm downstream from the anode surface. The energy spectrum of the ion beam was evaluated by a magnetic energy spectrometer. The ion energy was in reasonable good agreement with the acceleration voltage, that is, first pulse (negative pulse) voltage of the bipolar pulse.