bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecular Conductance through a Quadruple‐Hydrogen‐Bond‐Bridged Supramolecular Junction
Authors: Wang Lin , Gong Zhong‐Liang , Li Shu‐Ying , Hong Wenjing , Zhong Yu‐Wu , Wang Dong , Wan Li‐Jun
Published: August 2016

A series of self‐complementary ureido pyrimidinedione (UPy) derivatives modified with different aurophilic anchoring groups were synthesized. Their electron transport properties through the quadruple hydrogen bonds in apolar solvent were probed employing the scanning tunneling microscopy break junction (STMBJ) technique. The molecule terminated with a thiol shows the optimal electron transport properties, with a statistical conductance value that approaches 10−3 G0. The 1H NMR spectra and control experiments verify the formation of quadruple hydrogen bonds, which can be effectively modulated by the polarity of the solvent environment. These findings provide a new design strategy for supramolecular circuit elements in molecular electronics.
Aminopyridinyl–Pseudodeoxycytidine Derivatives Selectively Stabilize Antiparallel Triplex DNA with Multiple CG Inversion Sites
Authors: Okamura Hidenori , Taniguchi Yosuke , Sasaki Shigeki
Published: August 2016

The sequence‐specific formation of triplex DNA offers a potential basis for genome‐targeting technologies. In an antiparallel triplex DNA, the sequence‐specificity is established by the formation of specific base triplets (G−GC, A−AT, and T−AT) between a triplex‐forming oligonucleotide (TFO) and a duplex DNA. However, there are no natural nucleosides that can selectively recognize the inverted CG and TA base pairs. Therefore, the recognition of the CG and TA inversion sites to form a stable triplex DNA has been a long‐standing goal for the triplex‐forming technology. We now describe the design and synthesis of pseudo‐deoxycytidine (ΨdC) derivatives for selective recognition of the CG base pair to expand the triplex‐forming sequence. The aminopyridine‐bearing ΨdC derivatives showed high selectivity and affinity toward the CG base pair in all neighboring base contexts. Remarkably, 3‐methyl‐2‐aminopyridinyl−ΨdC (MeAP−ΨdC) formed a stable triplex with the promoter sequence of the hTERT gene containing four CG inversion sites, and effectively inhibited its transcription in human cancer cells. Thus, MeAP−ΨdC is expected to serve as a new starting point of triplex‐forming oligonucleotides for a wide variety of genome‐targeting applications.
Habitat recovery and restoration in aquatic ecosystems: current progress and future challenges
Authors: Geist Juergen , Hawkins Stephen J.
Published: August 2016

Aquatic ecosystems are degraded by a variety of pressures as a result of the growing human population. Global‐scale impacts include homogenization of biological communities, removal of top predators and ecosystem engineers, chemical pollution by excess nutrients and contaminants as well as deteriorating structural diversity, connectivity and process dynamics. There is a pressing societal need to reverse the decline in biodiversity and replace lost ecosystem functioning and services in aquatic ecosystems by enabling natural recovery or by active restoration.

Common concepts and approaches for conservation, recovery and restoration in freshwater and marine ecosystems, aided by recent advances in ecological theory, include decision criteria on priorities for conservation, harnessing natural recovery by cessation of impacts, restoring connectivity and meso‐habitat diversity as well as the geomorphological structural template including hydrodynamic processes. Re‐oligotrophication at catchment or regional sea‐scale benefits from integrating freshwater and marine restoration. Species or assemblages that convey biogenic structure or act as ecosystem engineers and keystone species should be given priority. Top‐down control can be reinstated in closed systems.

Differences between freshwater and marine ecosystems include the greater spatial restriction of many species in fresh water, the importance of rooted vegetation and insects in freshwater, and the much greater dispersal and connectivity in marine systems. These differences dictate different approaches, with more scope for active restoration work in fresh water and harnessing natural recovery in marine systems.

Restoration schemes need clearly defined target states. They should generally take a process‐oriented and stepwise adaptive management approach judging success against reference or control sites. Societal and political expectations need to be managed and restoration schemes should not promise too much. Even minor rehabilitation of degraded ecosystems can put back some biodiversity and key services. Sometimes ´Ersatz´‐ecosystems are better than nothing and the best that can be achieved, especially in urban settings.

Copyright © 2016 John Wiley & Sons, Ltd.
Geophysical and Archaeological Evidences of Buried Epipalaeolithic, Neolithic, Bronze Age and Roman Architecture in West‐Central Syria
Authors: Himi Mahjoub , Armendariz Angel , Teira Luis , González Jesus , Ibáñez Juan José , Haïdar‐Boustani Maya , Casas Albert
Published: August 2016

The study area is one of many important archaeological sites located near the city of Homs in Syria. Here, the existence of archaeological remains was studied using two complementary geophysical methods: ground‐penetrating radar (GPR) and electrical resistivity tomography (ERT). The results provide evidence of localized buried remains and allowed detailed pre‐excavation planning. Furthermore, the later archaeological excavations validated the results obtained from the GPR and ERT surveys. In some areas, the presence of moist clayey soils caused significant attenuation of the radar signal. Conversely, under these circumstances, the contrast in electrical resistivity between natural soil and archaeological targets is enhanced and thus the ERT results identified the archaeological remains.

Many two‐dimensional (2D) profiles showed a set of high relative resistivity values depicting well‐defined discontinuous structures within the first 2 m of depth. Nevertheless, their geometrical distribution and shape was much more clearly defined in the depth slice maps generated from the three‐dimensional (3D) blocks. As a result, data analysis provided a high‐resolution image of the subsurface distribution of the electrical resistivity properties of each area surveyed that can easily be interpreted in terms of structures of archaeological interest. Copyright © 2016 John Wiley & Sons, Ltd.
Solid Amine Adsorbent Prepared by Molecular Imprinting and Its Carbon Dioxide Adsorption Properties
Authors: He Hui , Zhuang Linzhou , Chen Shuixia , Liu Hucheng
Published: August 2016

A carbon dioxide imprinted solid amine adsorbent (IPEIA‐R) with polyethylenimine (PEI) as a skeleton was conveniently prepared by using glutaraldehyde to cross‐link carbon dioxide‐preadsorbed PEI. As confirmed by FTIR, FT‐Raman, and 13C NMR spectroscopy, CO2 preadsorbed on PEI could occupy the reactive sites of amino groups and act as a template for imprinting in the cross‐linking process. The imino groups formed from the cross‐linking reaction between glutaraldehyde and PEI could be reduced by NaBH4 to form CO2‐adsorbable amino groups. The adsorption results indicated that CO2 imprinting and reduction of imino groups by NaBH4 endowed the adsorbent with a higher CO2 adsorption capacity. Compared with PEI‐supported mesoporous adsorbents, the solid amine adsorbent with PEI as a skeleton can avoid serious pore blockage and CO2 diffusion resistance, even with a high amine content. The solid amine adsorbent with PEI as a skeleton showed a remarkable CO2 adsorption capacity (8.56 mmol g−1) in the presence of water at 25 °C, owing to the high amine content and good swelling properties. It also showed promising regeneration performance and could maintain almost the same CO2 adsorption capacity after 15 adsorption–desorption cycles.
Cover Image, Volume 10, Issue 5
Authors: Bezerra Tais Lacerda , Ragauskas Art J.
Published: August 2016

The cover image, by Arthur J. Ragauskas and Tais Lacerda Bezerra, is based on the Review A review of sugarcane bagasse for second‐generation bioethanol and biopower production, DOI: 10.1002/bbb.1662. Photo Courtesy: NREL image gallery and USDA/ARS image gallery.

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Fabrication of multilayered vascular tissues using microfluidic agarose hydrogel platforms
Authors: Kinoshita Keita , Iwase Masaki , Yamada Masumi , Yajima Yuya , Seki Minoru
Published: August 2016

Vascular tissues fabricated in vitro are useful tools for studying blood vessel‐related cellular physiologies and for constructing relatively large 3D tissues. An efficient strategy for fabricating vascular tissue models with multilayered, branched, and thick structures through the in situ hydrogel formation in fluidic channels is proposed. First, an aqueous solution of RGD‐alginate containing smooth muscle cells (SMCs) is introduced into channel structures made of agarose hydrogel, forming a cell‐embedding Ca‐alginate hydrogel layer with a thickness of several hundred micrometers on the channel surface because of the Ca2+ ions diffused from the agarose hydrogel matrix. Next, endothelial cells (ECs) are introduced and cultured for up to seven days to form hierarchically organized, multilayered vascular tissues. The factors affecting the thickness of the Ca‐alginate hydrogel layer, and prepared several types of microchannels with different morphologies are examined. The fabricated vascular tissue models are easily recovered from the channel by simply detaching the agarose hydrogel plates. In addition, the effect of O2 tension (20 or 80%) on the viability and elastin production of SMCs during the perfusion culture is evaluated. This technique would pave a new way for vascular tissue engineering because it enables the facile production of morphologically in vivo vascular tissue‐like structures that can be employed for various biomedical applications.
Enhanced cellulase production from Trichoderma reesei Rut‐C30 by engineering with an artificial zinc finger protein library
Authors: Zhang Fei , Bai Fengwu , Zhao Xinqing
Published: August 2016

Trichoderma reesei Rut‐C30 is a well‐known cellulase producer, and improvement of its cellulase production is of great interest. An artificial zinc finger protein (AZFP) library is constructed for expression in T. reesei Rut‐C30, and a mutant strain T. reesei U3 is selected based on its enhanced cellulase production. The U3 mutant shows a 55% rise in filter paper activity and 8.1‐fold increased β‐glucosidase activity, when compared to the native strain T. reesei Rut‐C30. It is demonstrated that enhanced β‐glucosidase activity was due to elevated transcription level of β‐glucosidase gene in the U3 mutant. Moreover, significant elevation in transcription levels of several putative Azfp‐U3 target genes is detected in the U3 mutant, including genes encoding hypothetical transcription factors and a putative glycoside hydrolase. Furthermore, U3 cellulase shows 115% higher glucose yield from pretreated corn stover, when compared to the cellulase of T. reesei Rut‐C30. These results demonstrate that AZFP can be used to improve cellulase production in T. reesei Rut‐C30. Our current work offers the establishment of an alternative strategy to develop fungal cell factories for improved production of high value industrial products.
Spectroscopic Properties of Apigenin in Various Bulk Solutions and Aerosol‐OT Reverse Micelles
Authors: Park Hyoung‐Ryun , Seo Jung‐Ja , Park Chul‐Ho , Yu Duan , Bark Ki‐Min
Published: August 2016

The fluorescence and ultraviolet (UV)/visible absorption spectra of apigenin (API) were measured and examined in bulk solutions and aerosol‐OT (AOT) reverse micelles. The Stokes’ shift in micelles is very small due to the small dipole moment change upon excitation. Since the intermolecular interaction between API and H2O in micelles is weak, the fluorescence parameters are relatively insensitive to the change in water concentration compared with those in bulk solutions. Since the B ring can rotate freely, the dihedral angle between the A, C, and B rings can be changed easily by the influence of the solvent. The potential energy curves of the electronic states show a very shallow or no minimum. Although the change in electronic energy by intermolecular interaction will be very small, the point where emission occurs on the energy curve can be altered very sensitively. Due to these reasons, the fluorescence properties of API are very sensitive to changes in excitation wavelength and solvent.
High Diastereoselectivity in the Yang Photocyclization via Remote Hydrogen Abstraction Reaction
Authors: Jang Mi , Park Bong Ser
Published: August 2016

1‐Benzoyl‐1‐(o‐alkoxyphenyl)cyclopropanes undergo Yang photocyclization to form dihydrobenzo‐pyranols in a stereospecific manner. The cyclopropyl group at alpha position to carbonyls gives not only a bias in the most stable geometries of the starting ketones but also conformational restriction on geometries of biradical intermediates. More importantly, intramolecular hydrogen bonds seem to give an additional effect on conformational control of the biradical reactivity.
Gender Diversity on Boards and Firms’ Environmental Policy
Authors: Li Ji , Zhao Fuqiang , Chen Silu , Jiang Wanxing , Liu Tao , Shi Shengping
Published: August 2016

This paper tests the relationship between gender diversity on boards and firms’ environmental policy. Based on prior research, we predict that gender diversity on boards of directors should have a positive relationship with firms’ environmental policy. Moreover, firm character in terms of pollution creation likelihood moderates the relationship between gender diversity on boards and firms’ environmental policy. Analyzing data from 865 publicly listed firms in the United States, we found direct and significant empirical evidence for our predictions. According to the findings, we highlight the importance of gender diversity for the development of good firm environmental policy as well as for the improvement of corporate governance. Moreover, the more likely firms in a given industry are to cause environmental pollution, the more salient will be the beneficial effect of gender diversity on boards on firms’ environmental policy in the industry. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Sustainable Entrepreneurship and B Corps
Authors: Stubbs Wendy
Published: August 2016

Sustainable entrepreneurship contributes to solving social and environmental problems through the means of successful for‐profit businesses. This paper contributes to understanding how sustainable entrepreneurship is implemented by exploring an emerging new form of business, ‘B Corps’, that employs market tactics to address social and environmental issues. Through interviewing 14 B Corps, the exploratory research study found that B Corps treat profit as a means to achieve positive societal ends, they regard the B Corp model as a tool for change, the B Corp model provides a common collective identity for internal and external validation, they are focused on societal impact rather than maximizing profits and they attempt to legitimate this form of sustainable entrepreneurship by influencing the business community and government officials. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Sustainability Strategy and Eco‐Innovation: A Moderation Model
Authors: Tsai Kuen‐Hung , Liao Yi‐Chuan
Published: August 2016

This study develops a moderation model to examine the role of a proactive environmental strategy on eco‐innovation. Drawing upon the perspectives of contingency theory, this study argues that the impacts of sustainability strategy on eco‐innovation depend on market demand, innovation intensity and government subsidy. The sample used to test the hypotheses is obtained from the Community Innovation Survey in Taiwan. A total of 2955 manufacturing firms are included in the final sample. A logit moderating regression is adopted to analyze the models. The results reveal that market demand and government subsidy positively moderate the relationship between environmental strategy and eco‐innovation. Specifically, firms are more likely to adopt a proactive environmental strategy to improve eco‐innovation under high levels of market demand and government subsidy. Furthermore, the results indicate that innovation intensity affects the effect of environmental strategy on eco‐innovation, but the direction of the influence varies with different categories of eco‐innovation. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Hip fractures in the elderly—A clinical anatomy review
Authors: Collin Peter G. , D'Antoni Anthony V. , Loukas Marios , Oskouian Rod J. , Tubbs R. Shane
Published: August 2016

As elderly populations rise worldwide, the amount of hip fractures have continued to increase and result in substantial medical burdens in many countries. This increase goes hand‐in‐hand with an increase in surgical procedures to correct hip fractures. The medical burden imparted by hip fractures and their corrective surgeries necessitate a clinically relevant understanding of the hip joint including the vascular, neural, and musculoskeletal structures directly associated with and neighboring the joint. It is critical to appreciate how the normal hip anatomy is disrupted by a fracture and how this disruption is heavily influenced by the fracture's location. The effects of advancing age on the integrity of the hip joint and the risk of hip fractures further complicate hip anatomy. Consequentially, normal hip anatomy, aging and the pathology introduced by fractures play major roles in how hip fractures are approached surgically. This article aims to review the clinically relevant anatomy of the healthy hip joint, age‐related changes that influence the joint, hip fractures, and corrective surgeries for hip fractures. Clin. Anat. 30:89–97, 2017. © 2016 Wiley Periodicals, Inc.
Anatomy, radiology, and practical procedure education for foundation doctors in England: A National Observational Study
Authors: Lewis Thomas L. , Sagmeister Markus L. , Miller George W. , Boissaud‐Cooke Matthew A. , Abrahams Peter H.
Published: August 2016

There are concerns regarding the anatomy knowledge amongst medical school graduates and foundation doctors. Clinical procedures performed without relevant anatomical knowledge could result in serious harm to patients. The aim of this quantitative study was to assess education provision in the domains of anatomy, radiology and practical procedures for foundation year doctors during their first two years of training (FY1, FY2). A national survey of acute hospital trusts in England was conducted. Each trust completed a proforma relating to education provision for foundation year doctors between 6/8/2014 and 4/8/2015. A total of 95/161 (59%) acute hospital trusts in England responded. The mean number of teaching hours/year was 55.6±19.0 for FY1 and 57.3±30.4 hours/year for FY2. Anatomy education was provided in eight trusts with a mean of 2.3±1.0 hours/year for FY1 and 2.7±2.0 hours/year for FY2. The mean provision of practical procedure education was 2.2±1.3 hours/year for FY1 and 2.7±4.4 hours/year for FY2. The mean provision of radiology education was 10.5±18.7 hours/year for FY1 and 7.8±14.2 hours/year for FY2. Reasons for the lack of teaching included: lack of time, facilities, teaching staff, financial resources and absence of specific educational domains in the foundation curriculum. Medical education provision for foundation doctors is highly variable. There are wide discrepancies in postgraduate anatomy education, procedural skill training and radiology education between hospital trusts. Clin. Anat. 29:982–990, 2016. © 2016 Wiley Periodicals, Inc.
Youth and the sociability of “Vaping”
Authors: Yule Jennifer A. , Tinson Julie S.
Published: August 2016

This article examines the contemporary and evolving social ritual of vaping (also known as the use and consumption of e‐cigarettes). This novel research finds a typology of users in a heterogeneous youth market and shows how the introduction of this new practice challenges existing ritual boundaries. Previous research has focused on the de‐marketing of tobacco and smoking cessation. Here, virtuous, dynamic, vulnerable, and invisible vapers are identified with each demonstrating differing levels of emotional engagement and characteristics of vaping behaviors. Utilizing Collins' theory of interaction rituals as a lens, this qualitative study explores the sociability of vaping practices to gain a deeper understanding of the enduring appeal of vaping and the subsequent consequences for youth “smoking” behaviors. While some vapers advocate the health benefits of this relatively new practice, the use of e‐cigarettes is also used as a form of resistance as well as mechanism for misbehavior. Copyright © 2016 John Wiley & Sons, Ltd.
Five‐Membered Cyclitol Phosphate Formation by a myo‐Inositol Phosphate Synthase Orthologue in the Biosynthesis of the Carbocyclic Nucleoside Antibiotic Aristeromycin
Authors: Kudo Fumitaka , Tsunoda Takeshi , Takashima Makoto , Eguchi Tadashi
Published: August 2016

Aristeromycin is a unique carbocyclic nucleoside antibiotic produced by Streptomyces citricolor. In order to elucidate its intriguing carbocyclic formation, we used a genome‐mining approach to identify the responsible enzyme. In silico screening with known cyclitol synthases involved in primary metabolism, such as myo‐inositol‐1‐phosphate synthase (MIPS) and dehydroqunate synthase (DHQS), identified a unique MIPS orthologue (Ari2) encoded in the genome of S. citricolor. Heterologous expression of the gene cluster containing ari2 with a cosmid vector in Streptomyces albus resulted in the production of aristeromycin, thus indicating that the cloned DNA region (37.5 kb) with 33 open reading frames contains its biosynthetic gene cluster. We verified that Ari2 catalyzes the formation of a novel five‐membered cyclitol phosphate from d‐fructose 6‐phosphate (F6P) with NAD+ as a cofactor. This provides insight into cyclitol phosphate synthase as a member of the MIPS family of enzymes. A biosynthetic pathway to aristeromycin is proposed based on bioinformatics analysis of the gene cluster.
A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone
Authors: Scherkus Christian , Schmidt Sandy , Bornscheuer Uwe T. , Gröger Harald , Kara Selin , Liese Andreas
Published: August 2016

A three‐step enzymatic reaction sequence for the synthesis of poly‐ϵ‐caprolactone (PCL) was designed running in a fed‐batch operation. The first part of the cascade consisted of two oxidation steps starting with alcohol dehydrogenase catalyzed oxidation from cyclohexanol to cyclohexanone and further oxidation to ϵ‐caprolactone (ECL) by means of a Baeyer–Villiger monooxygenase. As a third step, lipase‐catalyzed hydrolysis of the lactone to 6‐hydroxyhexanoic acid (6‐HHA) was designed. With this biocatalytic multistep process reported herein, severe substrate surplus and product inhibition could be circumvented by the fed‐batch operation by adding the cyclohexanol substrate and by in situ product removal of ECL by hydrolysis, respectively. Up to 283 mm product concentration of 6‐HHA was reached in the fed‐batch operated process without loss in productivity within 20 h. After extraction and subsequent polymerization catalyzed by Candida antarctica lipase B, analysis of the unfractionated polymer revealed a bimodal distribution of the polymer population, which reached a mass average molar mass (Mw) value of approximately 63 000 g mol−1 and a dispersity (Mw/Mn) of 1.1 for the higher molecular weight population, which thus revealed an alternative route to the conventional synthesis of PCL.
Multidrug‐Containing, Salt‐Based, Injectable Supramolecular Gels for Self‐Delivery, Cell Imaging and Other Materials Applications
Authors: Roy Rajdip , Dastidar Parthasarathi
Published: August 2016

Both molecular and crystal‐engineering approaches were exploited to synthesize a new class of multidrug‐containing supramolecular gelators. A well‐known nonsteroidal anti‐inflammatory drug, namely, indomethacin, was conjugated with six different l‐amino acids to generate the corresponding peptides having free carboxylic acid functionality, which reacted further with an antiviral drug, namely, amantadine, a primary amine, in 1:1 ratio to yield six primary ammonium monocarboxylate salts. Half of the synthesized salts showed gelation ability that included hydrogelation, organogelation and ambidextrous gelation. The gels were characterized by table‐top and dynamic rheology and different microscopic techniques. Further insights into the gelation mechanism were obtained by temperature‐dependent 1H NMR spectroscopy, FTIR spectroscopy, photoluminescence and dynamic light scattering. Single‐crystal X‐ray diffraction studies on two gelator salts revealed the presence of 2D hydrogen‐bonded networks. One such ambidextrous gelator (capable of gelling both pure water and methyl salicylate, which are important solvents for biological applications) was promising in both mechanical (rheoreversible and injectable) and biological (self‐delivery) applications for future multidrug‐containing injectable delivery vehicles.
Full Solution‐Processed Synthesis and Mechanisms of a Recyclable and Bifunctional Au/ZnO Plasmonic Platform for Enhanced UV/Vis Photocatalysis and Optical Properties
Authors: Hang Da‐Ren , Islam Sk Emdadul , Chen Chun‐Hu , Sharma Krishna Hari
Published: August 2016

The synthesis of noble metal/semiconductor hybrid nanostructures for enhanced catalytic or superior optical properties has attracted a lot of attention in recent years. In this study, a facile and all‐solution‐processed synthetic route was employed to demonstrate an Au/ZnO platform with plasmonic‐enhanced UV/Vis catalytic properties while retaining strengthened luminescent properties. The visible‐light response of photocatalysis is supported by localized surface plasmon resonance (LSPR) excitations while the enhanced performance under UV is aided by charge separation and strong absorption. The enhancement in optical properties is mainly due to local field enhancement effect and coupling between exciton and LSPR. Luminescent characteristics are investigated and discussed in detail. Recyclability tests showed that the Au/ZnO substrate is reusable by cleaning and has a long shelf life. Our result suggests that plasmonic enhancement of photocatalytic performance is not necessarily a trade‐off for enhanced near‐band‐edge emission in Au/ZnO. This approach may give rise to a new class of versatile platforms for use in novel multifunctional and integrated devices.
Catalytic Michael/Ring‐Closure Reaction of α,β‐Unsaturated Pyrazoleamides with Amidomalonates: Asymmetric Synthesis of (−)‐Paroxetine
Authors: Zhang Yu , Liao Yuting , Liu Xiaohua , Yao Qian , Zhou Yuhang , Lin Lili , Feng Xiaoming
Published: August 2016

A highly enantioselective tandem Michael/ring‐closure reaction of α,β‐unsaturated pyrazoleamides and amidomalonates has been accomplished in the presence of a chiral N,N′‐dioxide–Yb(OTf)3 complex (Tf: trifluoromethanesulfonyl) to give various substituted chiral glutarimides with high yields and diastereo‐ and enantioselectivities. Moreover, this methodology could be used for gram‐scale manipulation and was successfully applied to the synthesis of (−)‐paroxetine. Further nonlinear and HRMS studies revealed that the real catalytically active species was a monomeric L‐PMe2–Yb3+ complex. A plausible transition state was proposed to explain the origin of the asymmetric induction.
Experimentelle Parameterstudie zur Trockenzerkleinerung in Planetenkugelmühlen
Authors: Titscher Larissa , Breitung‐Faes Sandra , Kwade Arno
Published: August 2016

Planetenkugelmühlen sind aufgrund ihrer einfachen Handhabung und ihrer Eigenschaften, wie z. B. hohe Energiedichten, niedrige Anschaffungskosten und gute Reproduzierbarkeit der Ergebnisse, typische Mühlen für den Laborbetrieb. Obwohl Planetenkugelmühlen bereits seit vielen Jahren eingesetzt werden, sind die Parametereinflüsse auf die Zerkleinerung noch nicht ausreichend verstanden. In dieser Arbeit wird der Einfluss verschiedener Prozessparameter auf die Trockenzerkleinerung in Planetenkugelmühlen anhand der Zerkleinerung von Aluminiumoxid aufgezeigt. Eine empirische Parameterstudie zur Wahl günstiger Betriebsparameter wird präsentiert, mit deren Hilfe ein Prozessmodell entwickelt werden soll.
Bacterial Cell Growth Inhibitors Targeting Undecaprenyl Diphosphate Synthase and Undecaprenyl Diphosphate Phosphatase
Authors: Wang Yang , Desai Janish , Zhang Yonghui , Malwal Satish R. , Shin Christopher J. , Feng Xinxin , Sun Hong , Liu Guizhi , Guo Rey‐Ting , Oldfield Eric
Published: August 2016

We synthesized a series of benzoic acids and phenylphosphonic acids and investigated their effects on the growth of Staphylococcus aureus and Bacillus subtilis. One of the most active compounds, 5‐fluoro‐2‐(3‐(octyloxy)benzamido)benzoic acid (7, ED50∼0.15 μg mL−1) acted synergistically with seven antibiotics known to target bacterial cell‐wall biosynthesis (a fractional inhibitory concentration index (FICI) of ∼0.35, on average) but had indifferent effects in combinations with six non‐cell‐wall biosynthesis inhibitors (average FICI∼1.45). The most active compounds were found to inhibit two enzymes involved in isoprenoid/bacterial cell‐wall biosynthesis: undecaprenyl diphosphate synthase (UPPS) and undecaprenyl diphosphate phosphatase (UPPP), but not farnesyl diphosphate synthase, and there were good correlations between bacterial cell growth inhibition, UPPS inhibition, and UPPP inhibition.
Fine Tuning the Composition and Nanostructure of Fe‐Based Core–Shell Nanocatalyst for Efficient CO2 Hydrogenation
Authors: Gupta Sharad , Jain Vivek K. , Jagadeesan Dinesh
Published: August 2016

Hydrogenation of CO2 to hydrocarbons is one of the crucial technologies to address the energy deficit and increasing environmental pollution. In this work, we have synthesized and systematically studied the influence of composition and nanostructure of a Fe‐based, carbon‐coated core–shell nanocatalyst. The synthesis method offered good control over the thickness of the carbon coating in the core–shell catalyst, which in turn controlled the chemical composition of the core. The results emphasized an optimal amount of Fe3O4, Fe5C2 in the core and partially graphitized carbon in the shell for a high catalytic activity in the conversion of CO2 at atmospheric pressure with higher selectivity to C2‐C4 olefins.
Wetting angles of monovalent indium iodide on different substrates
Authors: Cröll Arne , Markert Jochen , Volz Martin , Ostrogorsky Aleksandar
Published: August 2016

Wetting angles of molten Indium monoiodide (InI) on two different substrates, fused silica and pyrolytic boron nitride (pBN), were measured and compared to literature values for carbon and ceramic aluminum oxide. pBN showed the highest value of 128.5°, versus 105° for fused silica. The latter also showed a strong decrease with temperature, similar to aluminium oxide. From the wetting angles and the known surface tension, the work of adhesion for both substrates was determined. A reaction of the pBN with InI precludes its use as a crucible, however, leaving fused silica as the best crucible choice.
Probing early heart development to instruct stem cell differentiation strategies
Authors: Calderon Damelys , Bardot Evan , Dubois Nicole
Published: August 2016

Scientists have studied organs and their development for centuries and, along that path, described models and mechanisms explaining the developmental principles of organogenesis. In particular, with respect to the heart, new fundamental discoveries are reported continuously that keep changing the way we think about early cardiac development. These discoveries are driven by the need to answer long‐standing questions regarding the origin of the earliest cells specified to the cardiac lineage, the differentiation potential of distinct cardiac progenitor cells, and, very importantly, the molecular mechanisms underlying these specification events. As evidenced by numerous examples, the wealth of developmental knowledge collected over the years has had an invaluable impact on establishing efficient strategies to generate cardiovascular cell types ex vivo, from either pluripotent stem cells or via direct reprogramming approaches. The ability to generate functional cardiovascular cells in an efficient and reliable manner will contribute to therapeutic strategies aimed at alleviating the increasing burden of cardiovascular disease and morbidity. Here we will discuss the recent discoveries in the field of cardiac progenitor biology and their translation to the pluripotent stem cell model to illustrate how developmental concepts have instructed regenerative model systems in the past and promise to do so in the future. Developmental Dynamics 245:1130–1144, 2016. © 2016 Wiley Periodicals, Inc.
Eutrophication strengthens the response of zooplankton to temperature changes in a high‐altitude lake
Authors: Li Yun , Xie Ping , Zhao Dandan , Zhu Tianshun , Guo Longgen , Zhang Jing
Published: August 2016

To assess whether and how zooplankton communities respond to variations in temperature and how these assemblages change with eutrophication, we performed a large‐scale, monthly survey from August 2011 to July 2012 to determine the seasonal and spatial variations in these communities in a high‐altitude lake. A detrended correspondence analysis and a path analysis demonstrated that temperature and chlorophyll a were important factors influencing zooplankton. The path diagram showed that Daphnia was negatively affected directly by chlorophyll a and indirectly by temperature, whereas Bosmina was directly and positively affected by temperature. Daphnia spp. decreased in both absolute and relative biomass during warm seasons, whereas Bosmina spp. showed the opposite trend. Moreover, the lowest Daphnia spp. biomass was observed in the southern region, which was the most eutrophic. Our results indicate that increasing temperatures will continue to shift the dominant genus from Daphnia to Bosmina, and this change will be exacerbated by eutrophication. In addition, the zooplankton of Lake Erhai have shifted to smaller species over time as temperature and eutrophication have increased, which implies that zooplankton succession to small cladocerans may be markedly accelerated under further climate change and the increased eutrophication that has been observed in recent decades.
Ghrelin and hormonal markers under exercise training in patients with heart failure with preserved ejection fraction: results from the Ex‐DHF pilot study
Authors: Trippel Tobias Daniel , Holzendorf Volker , Halle Martin , Gelbrich Götz , Nolte Kathleen , Duvinage Andre , Schwarz Silja , Rutscher Tinka , Wiora Julian , Wachter Rolf , Herrmann‐Lingen Christoph , Duengen Hans‐Dirk , Hasenfuß Gerd , Pieske Burkert , Edelmann Frank
Published: August 2016

Background

Over 50% of patients with symptomatic heart failure (HF) experience HF with preserved ejection fraction (HFpEF). Exercise training (ET) is effective in improving cardiorespiratory fitness and dimensions of quality of life in patients with HFpEF. A systemic pro‐inflammatory state induced by comorbidities as the cause of myocardial structural and functional alterations has been proposed in HFpEF. ET modifies myocardial structure and has been related to inflammatory state. We investigated Ghrelin, related adipokines, markers of inflammation, and neuro‐hormonal activation in patients undergoing a structured ET vs. usual care are with HFpEF.

Methods and results

Ex‐DHF‐P was a prospective, controlled, randomized multi‐centre trial on structured and supervised ET in patients with HFpEF. We performed a post hoc analysis in 62 patients from Ex‐DHF‐P. Ghrelin, adiponectin, leptin, IL‐1ß, IL‐6, IL‐10, tumour necrosis factor‐alpha, MR‐proANP, MR‐proADM, CT‐proET1, and CT‐proAVP were assessed to seize the impact of ET on these markers in patients with HFpEF. Thirty‐six (58%) patients were female, mean age was 64 years, and median ghrelin was 928 pg/mL (interquartile range 755–1156). When stratified for high versus low ghrelin, groups significantly differed at baseline in presence obesity, waist circumference, and adiponectin levels (P < 0.05, respectively). Overall, ghrelin levels rose significantly to 1013 pg/mL (interquartile range 813–1182) (P < 0.001). Analysis of covariance modelling for change in ghrelin identified ET (P = 0.013) and higher baseline adiponectin levels (P = 0.035) as influencing factors.

Conclusions

Exercise training tended to increase ghrelin levels in Ex‐DHF‐P. This increase was especially pronounced in patients with higher baseline adiponectin levels. Future trials are needed to investigate the effect of ET on endogenous ghrelin levels in regard to interactions with cardiac structure and clinically meaningful surrogate parameters.
Azaferrocene‐Based PNP‐Type Pincer Ligand: Synthesis of Molybdenum, Chromium, and Iron Complexes and Reactivity toward Nitrogen Fixation
Authors: Kuriyama Shogo , Arashiba Kazuya , Nakajima Kazunari , Tanaka Hiromasa , Yoshizawa Kazunari , Nishibayashi Yoshiaki
Published: August 2016

A series of azaferrocene‐based PNP‐type pincer ligands were designed and prepared as new PNP‐type pincer ligands. Some transition‐metal complexes, including molybdenum, chromium, and iron complexes, bearing these azaferrocene‐based PNP‐type pincer ligands were also prepared and characterized by X‐ray analysis. The stoichiometric and catalytic reactivities of molybdenum–dinitrogen complexes toward nitrogen fixation were investigated in detail.
Synthesis and Physical‐Chemical Properties of cis‐ and trans‐1‐Amino‐3‐fluoro‐3‐methylcyclobutanecarboxylic Acids
Authors: Chernykh Anton V. , Feskov Illia O. , Chernykh Alla V. , Kondratov Ivan S. , Tolmachova Nataliya , Radchenko Dmytro S. , Daniliuc Constantin G. , Haufe Günter
Published: August 2016

Hitherto unknown cis‐ and trans‐1‐amino‐3‐fluoro‐3‐methylcyclobutanecarboxylic acids were synthesized as pure diastereomers starting from diisopropyl 3‐oxocyclobutane‐1,1‐dicarboxylate. While pKa values of the carboxylic acid functions are the same for both stereoisomers (pKa = 2.80), the values for the amino groups are slightly different (8.46 or 8.77, respectively) presumably because of different interactions with the fluorine atoms.
Palladium‐Catalyzed C–H Arylation of Amides by Triazole Assistance
Authors: Santrač Darko , Cella Stefano , Wang Wei , Ackermann Lutz
Published: August 2016

Versatile palladium‐catalyzed C–H arylations of benzamides were accomplished with the assistance of a removable triazole amine (TAM). The robustness of the palladium‐catalyzed C–H functionalization protocol is reflected in its broad functional group tolerance, ample substrate scope, and ability to proceed under silver‐free reaction conditions.
Comparison of Different Synthesis Methods for LiNi0.5Mn1.5O4—Influence on Battery Cycling Performance, Degradation, and Aging
Authors: Börner Markus , Niehoff Philip , Vortmann Britta , Nowak Sascha , Winter Martin , Schappacher Falko M.
Published: August 2016

The high‐voltage spinel LiNi0.5Mn1.5O4 is one of the most promising candidates for use in high‐energy‐density lithium‐ion batteries. To investigate the influence of the synthesis method and the resulting particle morphology on the electrochemical performance, performance degradation, and aging, different synthesis routes for LiNi0.5Mn1.5O4 were evaluated in this study. Inhomogeneous transition metal cation intermixing and exposure to high temperatures during synthesis led to the formation of a small amount of impurities, which had a severe impact on the electrochemical performance. Furthermore, the particle morphology influences the electrolyte decomposition and the formation of the cathode electrolyte interphase (CEI) on the surface of particles. Moreover, transition metal dissolution was investigated by analyzing the Ni and Mn content in the electrolyte after constant current charge–discharge cycling. The results suggest that an unstable delithiated structure at high potentials leads to the dissolution of Mn and Ni into the electrolyte, whereas the particle morphology had only a minor influence on the extent of transition metal dissolution.
Mouse brain concentrations of α‐pinene, limonene, linalool, and 1,8‐cineole following inhalation
Authors: Satou Tadaaki , Hayakawa Mako , Kasuya Hikaru , Masuo Yoshinori , Koike Kazuo
Published: August 2016

The main volatile components of essential oils are monoterpenes. It is known that olfactory receptors recognize monoterpenes as a fragrance, and that they can affect emotions. On the other hand, the components of essential oils may act directly on the central nervous system as well as the olfactory nerve. However, the transport of monoterpenes to the brain following inhalation, which is the main method of administration in aromatherapy, is unclear. In this study, we investigated major monoterpenes of essential oils, such as (+)‐α‐pinene, (+)‐limonene, (‐)‐linalool, and 1,8‐cineole. After the inhalation of each compound, the mice brains were dissected, and brain extracts prepared with n‐hexane. The extracts were then subjected to gas chromatography‐mass spectrometry analysis. The results revealed that α‐pinene was transported to the brain maximally with 30 min inhalation, which may be due to its high volatility. Limonene and linalool showed maximal transport to the brain with 90 min inhalation. Brain concentrations of 1,8‐cineole showed minimal level after 30 min inhalation. Moreover, 1,8‐cineole was easily transported to the brain following intraperitoneal administration. These results could be applied as one of the indices for the effective use of essential oils in aromatherapy. Copyright © 2016 John Wiley & Sons, Ltd.
A density functional theory mechanistic study of thermal decomposition reactions of nitroethyl carboxylates: undermine of “pericyclic” insight
Authors: Kącka Agnieszka B. , Jasiński Radomir A.
Published: August 2016

Quantum chemical study of thermal decomposition reactions of model nitroethyl carboxylates were studied using various density functional theory levels. It was found that conversion esters into nitroalkenes demean according to one‐step mechanism. However, it is not an expected “pericyclic” mechanism but a “one‐step two‐stage” process. Subsequently, nitrous acid extrusion was also analyzed.
Perils of Polymorphism: Size Matters
Authors: Ward Michael D.
Published: August 2016

Since the discovery of polymorphism in 1832, the ability of molecular crystals to adopt different crystal forms has intrigued and frustrated the scientific community. Control of this property has been limited by poor understanding of nucleation pathways and the absence of methods that can intercept crystallization at its earliest stages. Nonetheless, polymorphism, a favorite subject of Jack Dunitz, who is honored in this special issue, has opened a window into the forces that govern molecular organization in the solid state, while enabling discovery of new crystal forms with improved properties. This review illustrates the growth of crystals in nanoscale reactors with sizes comparable with those for nucleation, where thermodynamics and kinetics intersect, changing polymorph stabilities, providing insights into nucleation, enabling discovery of new polymorphs, and even suggesting a route to disappearing polymorphs, brought to our attention by Dunitz and Bernstein twenty years ago.
EXAMINING PARENTS’ ROMANTIC ATTACHMENT STYLES AND DEPRESSIVE AND ANXIETY SYMPTOMS AS PREDICTORS OF CAREGIVING EXPERIENCES
Authors: River Laura M. , Borelli Jessica L. , Nelson‐Coffey S. Katherine
Published: August 2016

Evidence has suggested that parental romantic attachment style and depressive and anxiety symptoms are related to experiences of caregiving (Creswell, Apetroaia, Murray, & Cooper, 2013; Jones, Cassidy, & Shaver, 2014; Lovejoy, Graczyk, O'Hare, & Neuman, 2000), but more research is necessary to clarify the nature of these relations, particularly in the context of attachment‐salient events such as reunions. In a cross‐sectional study of 150 parents of children ages 1 to 3 years, we assessed participants’ attachment styles (self‐reported anxiety and avoidance) and depressive and anxiety symptoms. Participants generated a narrative describing their most recent reunion with their child, which we coded for caregiving outcomes of negative emotion and secure base script content. Attachment style and depressive and anxiety symptoms separately predicted each caregiving outcome. Depressive and anxiety symptoms mediated the associations between attachment style and caregiving outcomes. These results suggest that parental attachment insecurity and depressive and anxiety symptoms contribute to negative emotion and reduced secure base script content. Further, depressive and anxiety symptomatology partially accounts for the relation between attachment insecurity and caregiving outcomes, suggesting that parental mental health is a critical point for intervention.
Endothelial STAT3 Activation Increases Vascular Leakage Through Downregulating Tight Junction Proteins: Implications for Diabetic Retinopathy
Authors: Yun Jang‐Hyuk , Park Sung Wook , Kim Kyung‐Jin , Bae Jong‐Sup , Lee Eun Hui , Paek Sun Ha , Kim Seung U. , Ye Sangkyu , Kim Jeong‐Hun , Cho Chung‐Hyun
Published: August 2016

Vascular inflammation is characteristic feature of diabetic retinopathy. In diabetic retina, a variety of the pro‐inflammatory cytokines are elevated and involved in endothelial dysfunction. STAT3 transcription factor has been implicated in mediating cytokine signaling during vascular inflammation. However, whether and how STAT3 is involved in the direct regulation of the endothelial permeability is currently undefined. Our studies revealed that IL‐6‐induced STAT3 activation increases retinal endothelial permeability and vascular leakage in retinas of mice through the reduced expression of the tight junction proteins ZO‐1 and occludin. In a co‐culture model with microglia and endothelial cells under a high glucose condition, the microglia‐derived IL‐6 induced STAT3 activation in the retinal endothelial cells, leading to increasing endothelial permeability. In addition, IL‐6‐induced STAT3 activation was independent of ROS generation in the retinal endothelial cells. Moreover, we demonstrated that STAT3 activation downregulates the ZO‐1 and occludin levels and increases the endothelial permeability through the induction of VEGF production in retinal endothelial cells. These results suggest the potential importance of IL‐6/STAT3 signaling in regulating endothelial permeability and provide a therapeutic target to prevent the pathology of diabetic retinopathy. J. Cell. Physiol. 232: 1123–1134, 2017. © 2016 Wiley Periodicals, Inc.