bluuebunny/crossref_metadata_2025 huggingface dataset:
A study of mechanical properties of biobased epoxy network: Effect of addition of epoxidized soybean oil and poly(furfuryl alcohol)
Authors: Mashouf Roudsari Ghodsieh , Misra Manjusri , Mohanty Amar K.
Published: September 2016

A novel biobased thermoset interpenetrating network was introduced in this study. Epoxidized soybean oil (ESO) and poly(furfuryl alcohol) (PFA) were added to a commercial biobased epoxy resin. It was hypothesized that addition of ESO and PFA can decrease brittleness of bioepoxy resin and also increase biobased content. Mechanical properties of samples were evaluated using tensile and impact test. It was found that the addition of ESO and PFA increased notched Izod impact energy by 76.6%. This significant increase was related to incorporation of long flexible chains of ESO into the matrix. Hybridization of ESO and PFA in bioepoxy reduced tensile strength (around 70%), tensile modulus (around 90%), and glass transition temperature in comparison to neat bioepoxy. Tensile strength and modulus of hybridized system can be further improved by addition of natural fibers and the resultant composite may be considered as a good candidate for applications in which damping properties are important. Crosslink density was calculated using dynamic mechanical analysis and a decrease in crosslink density was observed in hybridized system. PFA domains were observed in the matrix using atomic force microscopy in peak force quantitative nano‐mechanical mode and it revealed inhomogeneity in the crosslinked structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44352.
A Robust Fault Estimation Scheme for a Class of Nonlinear Systems
Authors: Chua W. S. , Tan C. P. , Aldeen M. , Saha S.
Published: September 2016

This paper presents an observer‐based robust fault estimation scheme for a class of nonlinear systems. We consider the system where the fault enters both the state and output equations via unmeasurable nonlinear functions, for which currently no fault estimation scheme exists. The proposed scheme exploits the special structures and information embedded in the fault‐dependent nonlinear functions. We propose a design method to minimize the ℒ2 gain from the disturbances to the fault estimation, and provide conditions for the existence of such observers. The effectiveness of this scheme is demonstrated on a nonlinear single‐link flexible joint robot system with disturbances.
Orographic effect on tropical rain physics in the Asian monsoon region
Authors: Harikumar R.
Published: September 2016

Effect of orography on tropical rain drop size distribution (DSD), which was not well known, is evidenced through the present study. DSD is the number of raindrops/unit volume/diameter interval, which tells about the underlying physics of rainfall process. Rain DSD was studied, using a Joss–Waldvogel disdrometer, at three coastal and a hill station in the Tropics. The variation in the characteristics of three physically significant parameters derived from the DSD with rain rate clearly unraveled the effect of orography on rain physics. The orographic rain appears to have larger drops compared with nonorographic rains when rain rate is high.
Uniform sliced Latin hypercube designs
Authors: Chen Hao , Huang Hengzhen , Lin Dennis K. J. , Liu Min‐Qian
Published: September 2016

Sliced Latin hypercube designs (SLHDs) achieve maximum stratification in each dimension, but neither the full designs nor their slices can guarantee a good uniformity over the experimental region. Although the uniformity of the full SLHD and that of its slices are related, there is no one‐to‐one correspondence between them. In this paper, we propose a new uniformity measure for SLHDs by combining the two kinds of uniformity. Based on such a combined uniformity measure, the obtained uniform SLHDs have the design points evenly spread over the experimental region not only for the whole designs but also for their slices. Numerical simulation shows the effectiveness of the proposed uniform SLHDs for computer experiments with both quantitative and qualitative factors. Copyright © 2016 John Wiley & Sons, Ltd.
Verpacken, verkaufen, verschenken: Hans Sauters entomologische Praktiken zwischen Formosa und Europa, 1902–1914
Authors: Pannhorst Kerstin
Published: September 2016

Parcels, Sales and Gifts: Hans Sauter's Entomological Practices between Formosa and Europe, 1902–1914. The exploration of global biodiversity is a form of knowledge production that is necessarily specimen‐based. In the endeavor to chart the natural world, not only ideas and writings travelled across the oceans, but also a flood of scientific objects. The German entomologist Hans Sauter (1871–1943) spent most of his life in Formosa, then a Japanese colony. His pronounced aim was to complete an inventory of the entire fauna of Formosa. He aimed for the mass production of knowledge, becoming a collecting‐entrepreneur who employed scores of local collectors. Between 1902 and 1914, they amassed large quantities of insects, which required specialized practices in collecting, preserving, documenting, and packaging. Sauter sent these insects, but also hundreds of reptiles, mammals, birds, fish etc., to zoologists all over Europe who identified and published hitherto undescribed species. At first, Sauter sold his finds. Later, he stopped asking for money – pushing instead for speed in publication and making demands about the content and naming of these articles. His demands were met, especially by the Deutsches Entomologisches Museum in Dahlem. Despite almost no publications to his name, Sauter quickly gained considerable influence in the world of entomological research. In this paper, the circulation of these scientific objects serves as a focal point in order to embed local circumstances in the process of knowledge production in a global context. The practices associated with the specimens illustrate the economic, political and social dimensions of the formation of knowledge. Hans Sauter's case defies traditional dichotomies as it illustrates the interdependence of practical and theoretical knowledge, of science and trade and of center and periphery. Practical knowledge gained in a local setting in Formosa allowed Sauter to amass large amounts of insect specimens, a resource he used to steer the course of scientific practice in Europe.
Correlating blood and urinary concentrations of clobazam doses in Japanese children and adolescents with intractable epilepsy
Authors: Iwasaki Toshiyuki , Nonoda Yutaka , Ishida Tomoya , Toki Taira , Ishii Masahiro
Published: September 2016

Clobazam (CLB) is an antiepileptic drug that is metabolized to the major metabolite N‐desmethylclobazam (N‐CLB). Our aim was to evaluate the utility of corrected urinary concentrations of CLB and N‐CLB in Japanese children and adolescents with epilepsy. Blood and urinary concentrations of CLB and N‐CLB were evaluated in 42 patients. The urinary and peak blood concentrations were measured 2–3 h after the last dose. The ratio of the blood and urinary creatinine concentrations was used to calculate the corrected urinary concentrations. A moderate correlation was found between the CLB dose and the CLB serum concentration, but this correlation was not found for N‐CLB. Patients were dichotomized based on two regression lines, which were detected by statistical analyses with a cumulative distribution function: the lower ratio group (CLB/N‐CLB < 0.275) and the higher ratio group (≥0.275). Moderate correlations were observed between the CLB dose and the serum concentration or the corrected value of CLB for the lower ratio group, and moderate to strong correlations were observed for the higher ratio group. The corrected urinary concentration of CLB correlates to the CLB dose when stratified by the CLB/N‐CLB ratio and may prove practical for clinical estimation of the CLB serum concentration.
Cultivating Ecological Knowledge for Corporate Sustainability: Barilla's Innovative Approach to Sustainable Farming
Authors: Pogutz Stefano , Winn Monika I.
Published: September 2016

In this paper, we link three theoretical perspectives – organizational knowledge, ecological knowledge and social–ecological systems – to derive new conceptions of multi‐disciplinary, multi‐tier, sustainability‐oriented knowledge. Our study examines how collaboration between pasta‐producer Barilla, the farmers/smallholders supplying the firm and scientists generated sustainability practices in the agri‐food industry by creating transformative ecological, technical and scientific knowledge. In 2010, Barilla initiated a sustainable farming project to significantly reduce the environmental impact of cultivating durum wheat, its most important raw material. Core components included replacing monoculture with crop rotation, collectively creating innovative approaches that support farmers’ decision making and generating widely accessible guidelines for sustainability‐oriented cropping knowledge and practices. These collaborative efforts initiated profound transformations within and beyond the organization's boundaries via increased production yields, reduced environmental impacts and improved sustainability of farming practices, which generated economic, social and ecological benefits for farmers, surrounding communities and the firm. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Three‐dimensional analysis of talar trochlea morphology: Implications for subject‐specific kinematics of the talocrural joint
Authors: Nozaki Shuhei , Watanabe Kota , Katayose Masaki
Published: September 2016

Three‐dimensional (3D) behavior of the talocrural joint is primarily determined by the articular surface morphology of the talar trochlea and tibiofibular mortise. However, morphological features of the anterior and posterior regions of the talar trochlea remain unclear. The objectives of this study were to evaluate anterior and posterior radii of the medial and lateral talar trochlea and to estimate subject‐specific kinematics of the talocrural joint. Fifty dry tali were scanned using computed tomography to create 3D bone models. Radii of curvature of the anterior and posterior region at both the medial and lateral trochlea were calculated. Orientations of the dorsiflexion and plantarflexion axis passing through the centers of the circles fitted to the anterior region of the medial and lateral trochlea and through the centers of the circles fitted to the posterior region of the medial and lateral trochlea were evaluated, respectively. The anterior radius of the medial trochlea was significantly smaller than that of the lateral trochlea by a mean of 7.8 mm (P < 0.001). The posterior radius of the medial trochlea was larger than that of lateral trochlea in 30 samples (60%) and vice versa in 20 samples (40%). Unilateral asymmetric shape of anterior trochlea would induce external rotation of the talus during ankle dorsiflexion, whereas bilateral asymmetric shape of posterior trochlea would induce opposite axial rotations among subjects during ankle plantarflexion, which would help the physical therapists to restore talocrural joint motions to ideal state for patients with ankle injuries. Clin. Anat. 29:1066–1074, 2016. © 2016 Wiley Periodicals, Inc.
The orbit: A re‐appraisal of the surgical landmarks of the medial and lateral walls
Authors: Yoon Jisoo , Pather Nalini
Published: September 2016

The anterior ethmoidal foramen (AEF) and posterior ethmoidal foramina (AEF and PEF, respectively) on the medial wall and the cranio‐orbital foramen (COF) on the lateral wall are used as landmarks in orbital surgeries. In surgery these foramina, the neurovascular structures they transmit and other orbital structures in close proximity need to be identified to minimise their risk of damage. Despite the clinical importance, the current understandings lack consistency in the precise location, microanatomy and morphology of the foramina. This study therefore aimed to document and analyze the microanatomy, location, and morphometric relations of the EF and COF to determine a standardized guideline to accessing the foramina. One hundred dry orbits were morphometrically analyzed, and a further six orbits were micro‐dissected to determine the locations of the EF and COF. The orbital size dimensions were measured for each dry orbit and correlated with the morphometric distances. A complete morphometric and quantitative analysis showed the distances of the EF and COF to be variable, with greater variations observed in the incidence of the accessory EF and PEF distances in the medial wall, and in the presence of the COF and the accessory COF in the lateral orbital wall. Significant correlations were observed between the length of the medial orbital wall and some EF distances. This study is the first to suggest a standardized method of locating these foramina in the orbit irrespective of population and sex differences, in order to help improve clinical applications in crucial orbital surgeries. Clin. Anat. 29:998–1010, 2016. © 2016 Wiley Periodicals, Inc.
Up‐regulation of mir‐10b predicate advanced clinicopathological features and liver metastasis in colorectal cancer
Authors: Jiang Hong , Liu Jijun , Chen Yingtao , Ma Chong , Li Baosong , Hao Tao
Published: September 2016

Given the emerging role of microRNA in tumor disease progression, we investigated the association between miRNA 10b expression, liver metastasis, and clinicopathological of colorectal cancer (CRC). Two hundred and forty‐six pairs of samples (including CRC samples and normal adjacent tissues) from CRC patients were collected from May 2004 to May 2009. All samples verified to contain at least 80% tumor cells, and were immediately frozen in liquid nitrogen and stored at −80°C or fixed in 10% formalin for paraffin embedding. The expression of miRNA‐10b in CRC tissues was evaluated using a quantitative real‐time polymerase chain reaction RT‐PCR. Correlation between miR‐10b expression and poor clinicopathological of CRC patients were analyzed using Student's t‐tests and Chi‐square tests. A Kaplan–Meier survival curve was generated following a log‐rank test. miR‐10b expression was up‐regulated in CRC tissues (P < 0.0001) and in patients diagnosed as colorectal liver metastasis (CLM) at initial involvement or during follow‐up. When the Tumor Node Metastasis (TNM) stage was taken into consideration, the expression levels of miR‐10b were positively correlated with advanced TNM stages. In addition, the miR‐10b expression of patients diagnosed as CLM at initial involvement was significantly higher than those without liver metastasis (nCLM). Similarly, those patients developed with CLM during follow‐up (FCLM) was also markedly higher than those with nCLM. miR‐10b expression was also found correlated with advanced stage (P < 0.0001), lymph node metastasis (P = 0.025), venous infiltration (P = 0.007), poorer differentiation (P = 0.002), and served as an independent prognostic factor of poor overall survival (P < 0.0001). This study demonstrated the expression of miR‐10b had strong potential to serve as a noninvasive biomarker for CRC prognosis and predicting liver metastasis.
Metabolic Incorporation of Azide Functionality into Cellular RNA
Authors: Nainar Sarah , Beasley Samantha , Fazio Michael , Kubota Miles , Dai Nan , Corrêa Ivan R. , Spitale Robert C.
Published: September 2016

Real‐time tracking of RNA expression can provide insight into the mechanisms used to generate cellular diversity, as well as help determine the underlying causes of disease. Here we present the exploration of azide‐modified nucleoside analogues and their ability to be metabolically incorporated into cellular RNA. We report robust incorporation of adenosine analogues bearing azide handles at both the 2′‐ and N6‐positions; 5‐methylazidouridine was not incorporated into cellular RNA. We further demonstrate selectivity of our adenosine analogues for transcription and polyadenylation. We predict that azidonucleosides will find widespread utility in examining RNA functions inside living cells, as well as in more complex systems such as tissues and living animals.
Imidazolyl‐Naphthalenediimide‐Based Threading Intercalators of DNA
Authors: Suseela Y. V. , Das Shubhajit , Pati Swapan K. , Govindaraju T.
Published: September 2016

Intercalation by threading is anticipated to feature in DNA‐binding molecules for developing DNA‐targeted diagnostics and therapeutics. We investigated the role of an imidazolyl moiety in threading intercalators of DNA by employing a number of imidazolyl–naphthalenediimide conjugates. Threading intercalation was studied by UV spectroscopy, competitive binding fluorescent dye displacement, circular dichroism, isothermal calorimetry, and computational analysis. NIm6 was found to be a strong candidate, with good half‐life, as revealed by dissociation kinetic analysis. Computational studies supported intercalation of the naphthalene core between base pairs and binding of the imidazolyl moieties in the adjacent grooves (threading mechanism) through electrostatic and hydrogen‐bonding interactions. The interaction of the positively charged imidazolium moieties with the negatively charged phosphate backbone of DNA contributed to the favorable enthalpy change, as revealed by the experimental and computational data. Threading intercalation by NIm6 caused significant retardation of DNA in an electrophoretic mobility shift assay. The biological significance of potent imidazolyl naphthalenediimide conjugates was demonstrated by the inhibition of topo‐ isomerase I activity and cytotoxicity against HeLa cells.
Juvenile animal cruelty and firesetting behaviour
Authors: Baglivio Michael T. , Wolff Kevin T. , DeLisi Matt , Vaughn Michael G. , Piquero Alex R.
Published: September 2016

Background

There is a view that young people presenting with an animal cruelty and firesetting combination represent a uniquely risky group, but prior work has relied on samples with insufficient power.

Research question

What is the prevalence of the co‐occurrence of animal cruelty and firesetting behaviour among young delinquents? What other features correlate with this?

Methods

We measured the prevalence of animal cruelty and firesetting among 292,649 juvenile offenders and used rare events logistic regression to examine demographic, criminal, mental health and family histories as correlates.

Results

The prevalence of animal cruelty was 0.59%, accounting for 1732 young people, and of firesetting 1.56% (n = 4553). The co‐occurrence of these behaviours was rare: 0.17% (n = 498), but approximately twice that expected by chance based on the prevalence of each behaviour individually (0.59% × 1.56% = 0.009%). Rates were higher in males, older youths and Whites. Among historical variables, criminal history was the strongest correlate, followed by mental health problems, then familial and individual indicators.

Conclusions

As only male gender and being a victim of sexual abuse increased the odds of evidencing both animal cruelty and firesetting behaviour substantially above the odds for each behaviour individually, there thus appears to be little that is unique to the co‐occurrence. Our findings suggest that sensitivity to the occurrence of each is the best way forward, with rather familiar assessments and interventions offering some hope of reducing these seriously damaging behaviours. Copyright © 2016 John Wiley & Sons, Ltd.
Enhanced Electrokinetics of C−C Bond Splitting during Ethanol Oxidation by using a Pt/Rh/Sn Catalyst with a Partially Oxidized Pt and Rh Core and a SnO2 Shell
Authors: Yang Guangxing , Frenkel Anatoly I. , Su Dong , Teng Xiaowei
Published: September 2016

Direct ethanol fuel cells (DEFCs) are a promising technology for generating electricity through the electro‐oxidation of liquid ethanol. Its implementation requires the development of anode catalysts capable of producing CO2 and yielding 12‐electron transfer through breaking the C−C bond of ethanol. Here, we presented comprehensive studies of the electrokinetics of CO2 generation on Pt/Rh/Sn ternary catalysts. Our studies showed that the triphasic PtRhOx–SnO2 catalysts with a partially oxidized Pt and Rh core and a SnO2 shell, validated by X‐ray absorption analyses and scanning transmission electron microscope‐electron energy loss spectroscopy line scans, coincided with a 2.5‐fold increase in the CO2 generation rate towards ethanol oxidation reaction, compared with the biphasic PtRh‐SnO2 catalysts with a metallic PtRh alloy core and commercial Pt. These studies provided insight into the design of a new genre of electrocatalysts with a partially oxidized noble metal.
Orthogonal Palladium‐Catalyzed Direct C−H Bond Arylation of Heteroaromatics with Aryl Halides
Authors: Théveau Laure , Schneider Cédric , Fruit Corinne , Hoarau Christophe
Published: September 2016

Transition metal‐catalyzed direct C−H bond functionalization of heterocycles with halo(het)arenes has received considerable attention as synthetic alternative to standard cross‐coupling reactions regarding step‐ and atom‐economy in the preparation of heteroarylmetals intermediates and better chemo‐selectivity towards standard organic functions such as aldehyde, ketone, ester, cyanide, and amide. An additional major and poorly highlighted interest of such methodology is its unparalleled ability to open the chemical space of functionalization of heterocycles towards challenging unprecedented sites. This Review gives an overview of the advances in challenging orthogonal direct C−H arylation of heterocycles related to the wide variety of catalytic C−H bond metalation processes, most of them evaluated by DFT calculations.
Ammonia Decomposition over Nickel Catalysts Supported on Rare‐Earth Oxides for the On‐Site Generation of Hydrogen
Authors: Okura Kaname , Okanishi Takeou , Muroyama Hiroki , Matsui Toshiaki , Eguchi Koichi
Published: September 2016

Ammonia decomposition has attracted the interest of many researchers as a promising process for the on‐site generation of H2. In this study, Ni catalysts supported on various rare‐earth oxides were prepared by the impregnation method and employed for ammonia decomposition. The Ni/Y2O3 catalyst exhibited the best performance among the samples investigated. The reaction kinetics study indicated that most of rare‐earth oxide supports were effective for the alleviation of the hydrogen inhibition phenomenon in the decomposition reaction. The desorption behavior of hydrogen has revealed that the amount of hydrogen atoms adsorbed strongly on the Ni surface up to high temperatures was relatively small in the case of Ni/Y2O3. Furthermore, for Ni/Y2O3 the optimal Ni loading was 40 wt % in terms of the catalytic activity because of the appropriate Ni dispersion.
Highly Active and Coke‐Tolerant Hierarchical Mordenite Catalysts Synthesized by Recrystallization for the Isopropylation of Naphthalene
Authors: Lee Young Hye , Kim Won Yong , Park Hunmin , Choi Yo Han , Lee Jae Sung
Published: September 2016

In the isopropylation of naphthalene for the production of 2,6‐naphthalenedicarboxylate, the monomer of polyethylene naphthalate plastic, a shape‐selective mordenite (MOR) zeolite catalyst provides the best selectivity for the desired 2,6‐diisopropylnaphthalene. However, the small pore size of the zeolite limits the naphthalene conversion and lowers the stability because of pore‐mouth blocking by coke. We discovered that these problems could be mitigated by synthesizing a micro‐meso hierarchical pore structure in the MOR zeolite by the recrystallization of MOR with cetyltrimethylammonium bromide as a mesopore‐forming surfactant. The recrystallized catalysts allow the facile diffusion of bulky molecules through connected meso‐ and micropores to and from active catalytic sites located in the small MOR pores. Relative to microporous MOR, the hierarchical MOR catalyst demonstrated a greatly enhanced activity, stability, and coke tolerance, and the intrinsic high shape selectivity of MOR for 2,6‐diisopropylnaphthalene was maintained. Mild desilication enlarged the pore volume and formed additional acid sites to increase the activity further.
A Simple and Versatile Approach for the Fabrication of Paper‐Based Nanocatalysts: Low Cost, Easy Handling, and Catalyst Recovery
Authors: Montiel Laura , Delgado Jorge A. , Novell Marta , Andrade Francisco J. , Claver Carmen , Blondeau Pascal , Godard Cyril
Published: September 2016

A versatile method for the preparation of efficient and reusable nanocatalysts involving the painting of a commercial filter paper with a Pd@CNT (CNT=carbon nanotubes) ink was herein explored. The resulting paper‐based material provided excellent results in the semihydrogenation of alkynes and alkynols and could be recycled at least five times without loss of activity or selectivity.
Zirconium Oxide Supported Palladium Nanoparticles as a Highly Efficient Catalyst in the Hydrogenation–Amination of Levulinic Acid to Pyrrolidones
Authors: Zhang Jian , Xie Bin , Wang Liang , Yi Xianfeng , Wang Chengtao , Wang Guoxiong , Dai Zhifeng , Zheng Anmin , Xiao Feng‐Shou
Published: September 2016

The selective hydrogenation–amination of levulinic acid into pyrrolidones is regarded as one of the most important reactions to transform biomass‐derived lignocellulose feedstocks into valuable chemicals. Here we report on ZrO2‐supported Pd nanoparticles as a highly active, chemoselective, and reusable catalyst for the hydrogenation–amination of levulinic acid with H2 and various amines under mild reaction conditions. The Pd/ZrO2 catalyst exhibited a marked increase in activity compared with conventional Pd catalysts and a significant enhancement in pyrrolidone selectivity. The excellent catalytic performances are reasonably attributed to the ZrO2 support, which has strong Lewis acidity to enhance the hydrogenation–amination reaction and hinder side reactions.
Ligand‐Promoted Palladium‐Catalyzed C−H Acetoxylation of Simple Arenes
Authors: Valderas Carolina , Naksomboon Kananat , Fernández‐Ibáñez M. Ángeles
Published: September 2016

The palladium‐catalyzed C−H oxidation of simple arenes is an attractive strategy to obtain phenols, which have many applications in the fine chemicals industry. Although some advances have been made in this research area, low reactivity and selectivity are, in general, observed. This report describes a new catalytic system for the efficient C−H acetoxylation of simple arenes based on Pd(OAc)2 and a pyridinecarboxylic acid ligand.
Radial basis function neural networks based on projection pursuit approach and solvatochromic descriptors: single and full column prediction of gas chromatography retention behavior of polychlorinated biphenyls
Authors: Hassanzadeh Zeinabe , Ebrahimi Parastoo , Kompany‐Zareh Mohsen , Ghavami Raouf
Published: September 2016

The ultimate goal of projection methods is to search “interesting” projections in a low‐dimensional subspace that can uncover the natural structure of the data. The aim of this work is to compare the ability of projection pursuit (PP) and principal component analysis (PCA) in dimension reduction. For this purpose to be achieved, the scores of PP and PCA, by a different number of factors, were used as inputs of radial basis function (RBF) neural network. RBF neural network was used as a nonlinear regression method in a quantitative structure‐retention relationships study of 209 polychlorinated biphenyls (PCBs). The dependent variable was the high‐resolution gas chromatographic relative retention times of PCBs on 18 different stationary phases, and independent variables were solvatochromic solute descriptors. The results demonstrate that the dimension reduction ability of the PP is better than that of the PCA for both single and full column retention models.
Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?
Authors: Engesser Tobias A. , Friedmann Christian , Martens Arthur , Kratzert Daniel , Malinowski Przemysław J. , Krossing Ingo
Published: September 2016

A series of gold acetonitrile complexes [Au(NCMe)2]+[WCA]− with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO]+[WCA]− in acetonitrile ([WCA]−=[GaCl4]−, [B(CF3)4]−, [Al(ORF)4]−; RF=C(CF3)3). In the crystal structures, the [Au(NCMe)2]+ units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C−N stretching frequencies of [Au(NCMe)2]+ units). An attempt to prepare [Au(L)2]+ units, even with less weakly basic solvents like CH2Cl2, led to decomposition of the [Al(ORF)4]− anion and formation of [NO(CH2Cl2)2]+[F(Al(ORF)3)2]−. All nitrosyl reagents [NO]+[WCA]− were generated according to an optimized procedure and were thoroughly characterized by Raman and NMR spectroscopy. Moreover, the to date unknown species [NO]+[B(CF3)3CN]− was prepared. Its reaction with gold unexpectedly produced [Au(NCMe)2]+[Au(NCB(CF3)3)2]−, in which the cyanoborate counterion acts as an anionic ligand itself. Interestingly, the auroborate anion [Au(NCB(CF3)3)2]− behaves as a weakly coordinating counterion, which becomes evident from the crystallographic data and the vibrational spectral characteristics of the [Au(NCMe)2]+ cation in this complex. Ligand exchange in the only room temperature stable salt of this series, [Au(NCMe)2]+[Al(ORF)4]−, is facile and, for example, [Au(PPh3)(NCMe)]+[Al(ORF)4]− can be selectively generated. This reactivity opens the possibility to generate various [AuL1L2]+[Al(ORF)4]− salts through consecutive ligand‐exchange reactions that offer access to a huge variety of AuI complexes for gold catalysis.
Aseptic Zero Discharge Fluid Dynamic Gauging for Measuring the Thickness of Soft Layers on Surfaces
Authors: Wang Shiyao , Schlüter Florian , Gottschalk Nathalie , Scholl Stephan , Wilson D. Ian , Augustin Wolfgang
Published: September 2016

A bench‐top device that can be used to perform fluid dynamic gauging measurements of soft solid layers with zero net liquid discharge and potentially under aseptic (closed system) conditions is demonstrated. Test results are presented for Newtonian liquids with a range of viscosities: deionized water, sucrose solutions, glycerol/water solutions and paraffin oil. The experimental data for discharge coefficient Cd against clearance/nozzle throat diameter gave good agreement with CFD simulations and literature. The influence of surface roughness was studied by making measurements on a series of commercial sandpapers. The rough surfaces gave rise to systematic differences in Cd from those obtained with smooth substrates. Careful calibration is required when gauging rough surfaces.
Direct Correlation between Molecular Cross‐linking and Macroscopic Mechanical Properties for Green Solids of Deoxyribonucleic Acids
Authors: Morimitsu Yuma , Matsuno Hisao , Ohta Noboru , Sekiguchi Hiroshi , Tanaka Keiji
Published: September 2016

Double‐stranded deoxyribonucleic acids (DNAs) were intermolecularly cross‐linked using 2,5‐hexanedione under reductive amination conditions in aqueous phase. Cross‐linking points between DNAs were directly observed by atomic force microscopy in conjunction with a conventional gel electrophoresis analysis. While DNA chains near cross‐linking points were denatured, DNA chains not near cross‐linking points maintained B‐form double strands. A transparent and self‐supported film of cross‐linked DNA (DNA‐c) was obtained by a simple solvent‐casting method. The tensile properties of DNA‐c films were much better than those of non‐cross‐linked DNA (DNA‐n) films due to the presence of the cross‐linking portions. Structural analyses based on wide‐angle X‐ray diffraction measurements revealed that the reorientation of DNA‐c was remarkably restricted by the introduction of cross‐linking points.
Free Energy of Bare and Capped Gold Nanoparticles Permeating through a Lipid Bilayer
Authors: Mhashal Anil R. , Roy Sudip
Published: September 2016

Herein, we study the permeation free energy of bare and octane‐thiol‐capped gold nanoparticles (AuNPs) translocating through a lipid membrane. To investigate this, we have pulled the bare and capped AuNPs from bulk water to the membrane interior and estimated the free energy cost. The adsorption of the bare AuNP on the bilayer surface is energetically favorable but further loading inside it requires energy. However, the estimated free‐energy barrier for loading the capped AuNP into the lipid membrane is much higher compared to bare AuNP. We also demonstrate the details of the permeation process of bare and capped AuNPs. Bare AuNP induces the curvature in the lipid membrane whereas capped AuNP creates an opening in the interacting monolayer and get inserted into the membrane. The insertion of capped AuNP induces a partial unzipping of the lipid bilayer, which results in the ordering of the local lipids interacting with the nanoparticle. However, bare AuNP disrupts the lipid membrane by pushing the lipid molecules inside the membrane. We also analyze pore formation due to the insertion of capped AuNP into the membrane, which results in water molecules penetrating the hydrophobic region.
Two‐Step Mechanochromic Luminescence of N,N′‐Bis‐Boc‐3,3′‐di(pyren‐1‐yl)‐2,2′‐biindole
Authors: Ito Suguru , Yamada Takeshi , Asami Masatoshi
Published: September 2016

Despite recent advances in the development of mechanochromic luminescent organic molecules, the mechano‐responsive properties of intramolecularly stacked fluorophores are not well documented. Herein, the synthesis and emission properties of three N,N′‐bis‐Boc‐3,3′‐diaryl‐2,2′‐biindole (Boc=tert‐butoxycarbonyl) derivatives as a new class of solid‐state emissive fluorophores are described. For a 3,3′‐dipyrenyl derivative in the crystalline state, partial intramolecular stacking of the dipyrenyl groups was observed, which results in a two‐step mechanochromic luminescence from blue (λem=462 nm) to green (λem=516 nm) and yellow (λem=535 nm).
S‐Adenosyl Methionine in the Therapy of Depression and Other Psychiatric Disorders
Authors: Karas Kuželički Nataša
Published: September 2016

Preclinical Research

S‐adenosyl methionine (SAM) is a major methyl donor and as such exerts its influence on CNS function through methylation reactions, such as methylation of several catecholamine moiety‐containing neurotransmitters, epigenetic changes through methylation of DNA, RNA, RNA‐binding proteins and histones, and phospholipid methylation. Based on available evidence, SAM is currently recommended as a next‐step (second‐line) treatment option following inadequate treatment response to a first‐line antidepressant. It shows significant promise in the treatment of pediatric and perinatal depression, as well as Alzheimer's disease, but to make this a recommendation further clinical trials are needed. SAM is safe to use in most patients, but is contraindicated in those with bipolar disorder. Concerns considering the possible increase of homocysteine levels (and cardiovascular complications) due to long‐term SAM therapy need to be further addressed in clinical trials taking into account individual`s ability to metabolize homocysteine and his/her folate status. Drug Dev Res 77 : 336–346, 2016. © 2016 Wiley Periodicals, Inc.
Bridging two scholarly islands enriches both: COI DNA barcodes for species identification versus human mitochondrial variation for the study of migrations and pathologies
Authors: Thaler David S. , Stoeckle Mark Y.
Published: September 2016

DNA barcodes for species identification and the analysis of human mitochondrial variation have developed as independent fields even though both are based on sequences from animal mitochondria. This study finds questions within each field that can be addressed by reference to the other. DNA barcodes are based on a 648‐bp segment of the mitochondrially encoded cytochrome oxidase I. From most species, this segment is the only sequence available. It is impossible to know whether it fairly represents overall mitochondrial variation. For modern humans, the entire mitochondrial genome is available from thousands of healthy individuals. SNPs in the human mitochondrial genome are evenly distributed across all protein‐encoding regions arguing that COI DNA barcode is representative. Barcode variation among related species is largely based on synonymous codons. Data on human mitochondrial variation support the interpretation that most – possibly all – synonymous substitutions in mitochondria are selectively neutral. DNA barcodes confirm reports of a low variance in modern humans compared to nonhuman primates. In addition, DNA barcodes allow the comparison of modern human variance to many other extant animal species. Birds are a well‐curated group in which DNA barcodes are coupled with census and geographic data. Putting modern human variation in the context of intraspecies variation among birds shows humans to be a single breeding population of average variance.
Fifteen‐year trends in the management of cardiogenic shock and associated 1‐year mortality in elderly patients with acute myocardial infarction: the FAST‐MI programme
Authors: Aissaoui Nadia , Puymirat Etienne , Juilliere Yves , Jourdain Patrick , Blanchard Didier , Schiele François , Guéret Pascal , Popovic Batric , Ferrieres Jean , Simon Tabassome , Danchin Nicolas
Published: September 2016

Aims

Alhough cardiogenic shock (CS) after acute myocardial infarction (AMI) is more common in elderly patients, information on the epidemiology of these patients is scarce. This study aimed to assess the trends in prevalence, characteristics, management, and outcomes of elderly patients admitted with CS complicating AMI between 1995 and 2010, using data from the FAST‐MI programme.

Methods and results

We analysed the incidence and 1‐year mortality of CS in four nationwide French surveys carried out 5 years apart from 1995 to 2010, including consecutive AMI patients over 1‐month periods. Among the 10 610 patients, 3389 were aged ≥75 years, of whom 9.9% developed CS. The prevalence of CS decreased in elderly patients from 11.6% in 1995 to 6.7% in 2010 (P = 0.02). Over the 15‐year period, the characteristics of elderly patients with CS changed, with more diabetes, hypertension, and hypercholesterolaemia. The use of PCI increased markedly in elderly patients with and without CS, reaching 51% and 59%, respectively, in 2010. In addition, medical therapy also evolved, with more patients receiving antithrombotic agents, beta‐blockers, and statins. Over time, 1‐year mortality decreased by 32% among elderly patients with CS but remained high (59% in 2010). ST‐segmet elevation myocardial infarction and previous AMI were independent correlates of increased 1‐year death, while study period was associated with decreased mortality (2010 vs, 1995: hazard ratio 0.40, 95% confidence interval 0.27–0.61, P < 0.001), along with early use of PCI.

Conclusion

Cardiogenic shock in elderly patients with AMI remains a major clinical concern. However, 1‐year mortality declined in these patients, a decrease potentially mediated by broader use of PCI and the improvement of global patient management.
Chronic Trichuris muris infection alters hematopoiesis and causes IFN‐γ‐expressing T‐cell accumulation in the mouse bone marrow
Authors: Chenery Alistair L. , Antignano Frann , Hughes Michael R. , Burrows Kyle , McNagny Kelly M. , Zaph Colby
Published: September 2016

Proinflammatory cytokines produced during immune responses to infectious stimuli are well‐characterized to have secondary effects on the function of hematopoietic progenitor cells in the BM. However, these effects on the BM are poorly characterized during chronic infection with intestinal helminth parasites. In this study, we use the Trichuris muris model of infection and show that Th1 cell‐associated, but not acute Th2 cell‐associated, responses to chronic T. muris infection cause a major, transient expansion of CD48−CD150− multipotent progenitor cells in the BM that is dependent on the presence of adaptive immune cells and IFN‐γ signaling. Chronic T. muris infection also broadly stimulated proliferation of BM progenitor cells including CD48−CD150+ hematopoietic stem cells. This shift in progenitor activity during chronic T. muris infection correlated with a functional increase in myeloid colony formation in vitro as well as neutrophilia in the BM and peripheral blood. In parallel, we observed an accumulation of CD4+, CD8+, and CD4−CD8− (double negative) T cells that expressed IFN‐γ, displaying activated and central memory‐type phenotypes in the bone marrow during chronic infection. Thus, these results demonstrate that Th1 cell‐driven responses in the intestine during chronic helminth infection potently influence upstream hematopoietic processes in the BM via IFN‐γ.
High Gas Adsorption Capacity of an agw‐Type Metal–Organic Framework Decorated with Methyl Groups
Authors: Du Liting , Lu Zhiyong , Xu Li , Ma Mengtao , Zhang Jinchi
Published: September 2016

A new methyl‐functionalized metal–organic framework, {Cu3(CMPEIP)2·2H2O}n {m‐NB13, H3CMPEIP = 5‐[(4‐carboxy‐2‐methylphenyl)ethynyl]isophthalic acid} was solvothermally synthesized and structurally characterized. {Cu3(CMPEIP)2·2H2O}n exhibits a high BET surface area of 3215.4 m2 g–1, a large H2 uptake (1.92 wt.‐% at 0.1 MPa and 77 K), and excellent CO2 storage capacity (9.24 wt.‐% at 0.1 MPa and 298 K).
Siamese‐Twin Porphyrins: Variation of Two meso‐Aryl Groups
Authors: Mitevski Oliver , Dechert Sebastian , Brückner Christian , Meyer Franc
Published: September 2016

Variation of two out of the six meso‐aryl groups in Siamese‐twin porphyrin, an expanded porphyrin incorporating two pyrazole moieties, identified a set of substituents that result in optimized preparation of highly crystalline products. Electron‐donating and electron‐withdrawing aryl substituents have only negligible electronic and structural influences on the free‐base macrocycles (as measured by their UV/Vis absorption spectra and solid‐state structures, respectively) and their dicopper complexes (as measured by their cyclic voltammograms).
Borylative Cyclization Reactions
Authors: Buñuel Elena , Cárdenas Diego J.
Published: September 2016

Borylative cyclizations constitute a family of important cascade reactions for the formation of carbo‐ and heterocycles containing boryl substituents. These compounds are formed from a variety of starting mono‐ and polyunsaturated substrates in metal‐catalyzed or boron‐mediated processes, and can be employed in subsequent functionalization. Here we review recently reported borylative cyclization reactions with special emphasis on metal‐catalyzed processes. These may involve the formation of one or several rings and the formation of a C–B bond in a domino process taking place within the same synthetic operation.
Total Syntheses of Vellosimine, N‐Methylvellosimine, and 10‐Methoxyvellosimine and Formal Synthesis of 16‐Epinormacusine B through a [5+2] Cycloaddition
Authors: Krüger Sebastian , Gaich Tanja
Published: September 2016

To date, more than 100 members of the sarpagine alkaloid family have been isolated. Their structural variations originate from oxidative transformations of the carboskeleton and the presence of both absolute configurations at the C‐16 atom, which is established in the course of their biosynthesis. More than 40 sarpagine alkaloids belong to the either the 16‐regular or 16‐epi subgroups, depending on the stereochemistry at C‐16. Herein, we report the formal synthesis of 16‐epinormacusine B, a member of the 16‐epi group, by using our well‐established generalized strategy for the total synthesis of these alkaloids. Furthermore, we provide the synthetic details and pitfalls of the asymmetric total syntheses of vellosimine, N‐methylvellosimine, and 10‐methoxyvellosimine, all members of the 16‐regular group.
Analytical Approach for Evaluation of Lithium‐Ion Battery Cells
Authors: Wagner Sebastian , Oberland Alexander , Turek Thomas
Published: September 2016

A new method for evaluation of battery cells containing porous thin‐layer electrodes is developed. For this purpose, a typical concept of chemical reaction engineering to classify reactors by dimensionless characteristic values is used. Therefore, the system of equations describing the porous electrodes in a battery cell is transferred to dimensionless notation and corresponding dimensionless properties are developed. The required kinetic data are measured with the help of electrochemical test cells. A complete set of parameters for the description of the lithium‐ion battery is determined and the characteristic properties for the chosen example are calculated and analyzed. Finally, the performance of the anode and cathode using lithium manganese oxide and surface‐modified graphite as active materials is compared with the aid of the newly developed dimensionless parameters.
Improved Electrochemical Performance of Modified Mesocarbon Microbeads for Lithium‐Ion Batteries Studied using Solid‐State Nuclear Magnetic Resonance Spectroscopy
Authors: Bösebeck Katharina , Chandran C. Vinod , Licht Björn K. , Binnewies Michael , Heitjans Paul
Published: September 2016

Lithium‐intercalating materials such as graphite are of great interest, especially for application in lithium‐ion batteries. In this work we present an investigation of the electrochemical performance of mesocarbon microbeads (MCMB) modified with copper to reveal the basic electrochemical mechanisms. Copper‐modified graphite is known to have better long‐term cycling behavior as well as higher capacity compared to the pristine material. Several reasons for these effects were postulated but not proven. Solid‐state nuclear magnetic resonance (NMR) spectroscopy provides structural and dynamic information on lithium in ionic conductors. To elucidate the changes in structure and dynamics for the pristine and the modified material, we have employed multi‐nuclear solid‐state NMR spectroscopy as well as 7Li spin‐lattice relaxation measurements and were able to clarify some reasons for the improved characteristics of copper‐modified graphite compared to the pristine material, which include increased solid–electrolyte interface (SEI) formation, a facilitated diffusion of lithium ions through the SEI, and reduced moisture.
Enriched Doping Level and Tuned Fiber Fractal Dimensions in Nonwoven Carbon‐Doped Polyaniline for Efficient Solid‐State Supercapacitors
Authors: Kumar Niraj , Sahoo Prasanta K. , Panda Himanshu S.
Published: September 2016

Nonwoven fibrous mats of polyaniline/carbon black on conducting substrates are synthesized through a two‐step oxidative process. Adsorbed and catalyzed aniline monomers in the synthesis process improved the doping degree (0.381) in the hybrid fibers. The formation of a porous mat on substrates was confirmed by using electron microscopy and small‐angle X‐ray scattering. The fractal dimensions of the fibers are correlated with Porod's law and suggest the presence of a nonfractal structure in the PCN1 mat. The hybrid mat exhibited a high porosity and effective surface area, even interfaces, and conductive pathways for the electrode/electrolyte to improve the kinetic process. Electrochemical measurements have been conducted on developed fibers, which showed a high specific capacitance of around 1526 F g−1, excellent cyclic stability, and elevated energy density (212 Wh kg−1) after doping carbon into polyaniline (PANI). Additionally, a symmetric solid‐state supercapacitor device was fabricated, a capacitance around 270 F g−1 was measured, and it was able to light a commercial light‐emitting diode (LED).