bluuebunny/crossref_metadata_2025 huggingface dataset:
Commentary on “O3 variability in the troposphere as observed by IASI over 2008–2016: Contribution of atmospheric chemistry and dynamics” by Wespes et al.
Authors: Payne Vivienne H. , Neu Jessica L. , Worden Helen M.
Published: May 2017

Evaluation and attribution of variability and trends in tropospheric ozone requires consideration not only of the spatial distribution of ozone precursor emissions and their changes in time but also of variations in transport at regional and global scales. Satellite measurements of tropospheric ozone are now beginning to provide the vertical resolution, length of record, and density of coverage needed for disentangling the factors that influence variability and trends. A recent study by Wespes et al. (2017, https://doi.org/10.1002/2016JD025875), utilizing an 8 year data set from the Infrared Atmospheric Sounding Instrument (IASI) satellite instrument to perform a global scale, spatially resolved analysis of influences of geophysical drivers on tropospheric ozone variability, represents a key step toward understanding long‐term changes in the distribution of tropospheric ozone and its corresponding impacts on air quality, chemistry, and climate.
Detection of a hydrogen corona at Callisto
Authors: Roth Lorenz , Alday Juan , Becker Tracy M. , Ivchenko Nickolay , Retherford Kurt D.
Published: May 2017

In December 2001, the Space Telescope Imaging Spectrograph of the Hubble Space Telescope obtained far‐ultraviolet spectral images of Jupiter's moon Callisto. The leading and trailing hemispheres were observed in the spectral range 1190 Å to 1720 Å when the moon was at eastern and western elongations, respectively. We analyzed the hydrogen Lyman α (1216 Å) signal in the two observations and found that faint atmospheric emissions extending up to several moon radii away are present in addition to the solar flux reflected off the surface. We show that the detected atmospheric Lyman α emissions are consistent with an escaping hydrogen corona with a vertical column density in the range of (6–12) ×1011 cm−2. The derived hydrogen abundance is about 2 times higher when the moon is at eastern elongation, possibly related to increased water sublimation when the visibly darker leading hemisphere is illuminated by the Sun. The detected hemispheric difference is larger than the measurement uncertainties providing first evidence for variations in Callisto's neutral atmosphere.
Investigation of the possible effects of comet Encke's meteoroid stream on the Ca exosphere of Mercury
Authors: Plainaki Christina , Mura Alessandro , Milillo Anna , Orsini Stefano , Livi Stefano , Mangano Valeria , Massetti Stefano , Rispoli Rosanna , De Angelis Elisabetta
Published: May 2017

The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) observations of the seasonal variability of Mercury's Ca exosphere are consistent with the general idea that the Ca atoms originate from the bombardment of the surface by particles from comet 2P/Encke. The generating mechanism is believed to be a combination of different processes including the release of atomic and molecular surface particles and the photodissociation of exospheric molecules. Considering different generation and loss mechanisms, we perform simulations with a 3‐D Monte Carlo model based on the exosphere generation model by Mura et al. (2009). We present for the first time the 3‐D spatial distribution of the CaO and Ca exospheres generated through the process of micrometeoroid impact vaporization, and we show that the morphology of the latter is consistent with the available MESSENGER/Mercury Atmospheric and Surface Composition Spectrometer observations. The results presented in this paper can be useful in the exosphere observations planning for BepiColombo, the upcoming European Space Agency‐Japanese Aerospace Exploration Agency mission to Mercury.
Glycosyltransferases of the
GT
43 Family
Authors: Anders Nadine , Dupree Paul
Published: May 2017

Members of the CAZy family GT43 are present in the plant and animal kingdoms. Two members of the Arabidopsis GT43 family, IRX9 and IRX14, are suggested to act as β‐1,4‐xylosyltransferases, transferring UDP‐Xyl to xylosyloligomers, a process required for glucoronoxylan (GX) synthesis. Absence of IRX9 or IRX14 leads to a decrease in xylan chain length and reduced xylose content of cell walls. The mutant plants exhibit collapsed xylem vessels and, in the case of
irx9
, dwarfed plant growth. However, the enzymatic activity of the purified proteins remains to be demonstrated, as does the function of most plant GT43 family members. Interestingly, all animal GT43 proteins studied so far catalyse a different enzymatic reaction. They act as β‐1,3‐glucuronosyltransferases transferring GlcA to a terminal Gal residue of diverse carbohydrate epitopes and are involved in the synthesis of proteoglycans, glycoproteins and/or glycolipids. Thus, GT43 proteins likely diversified in evolution in order to facilitate related, but not identical, biochemical reactions involved in different biological processes, adjusting the properties of the plant cell wall and the animal extracellular matrix to the specific requirements in the two kingdoms.
The Plant Glycosyltransferase FamilyGT64: In Search of a Function
Authors: Edvardsson Ellinor , Singh Sunil Kumar , Yun Min‐Soo , Mansfeld Agata , Hauser Marie‐Theres , Marchant Alan
Published: May 2017

The glycosyltransferase 64 (GT64) family includes members from a diverse range of species including human, Xenopus and Drosophila as well as plant species including Arabidopsis, the moss Physcomitrella and poplar. The majority of the animal GT64 proteins are bimodular, consisting of an N‐terminal GT47 domain linked to a GT64 domain. The animal GT64 domain has been found to have GlcNAc transferase activity and functions during heparan sulphate biosynthesis. However, the biochemical activity of the plant GT64 proteins has yet to be established. Arabidopsis has three GT64 members which have been named ECTOPICALLY PARTING CELLS1 (EPC1), EPC‐LIKE1 (EPC‐L1) and EPC‐LIKE2 (EPC‐L2). The EPC1 and EPC‐L1 proteins are comprised of a single GT64 domain whereas the EPC‐L2 protein has an additional N‐terminal domain which does not show homology to any other protein other than EPC‐L2 homologues from other plants. Mutation of the Arabidopsis GT64 EPC1 results in a plant with severely reduced stature, demonstrating the importance of its function for normal plant development. Neutral sugar analysis of theepc1cell wall shows a reduction in galactose but there is currently no enzymatic activity demonstrated to explain this alteration. In contrast to EPC1, EPC‐L2 is specifically expressed in reproductive tissues and mutations in the gene result in defects in pollen development, reduced seed formation and embryo abortions at the late globular stage.
Quantitative Genetics and Genomics of Plant Resistance to Insects
Authors: Kliebenstein Daniel J
Published: May 2017

Insects can cause significant damage to plants, both in agricultural and natural settings that lead to significant losses in yield or fitness. This has led plants to develop a large number of different defence mechanisms and strategies, from chemical toxin production to the generation of defence structures such as trichomes. The vast majority of these structures and mechanisms show genetic variation both within and between plant species, because of the vast number of different insects that a plant must fend off, each with their own mode of attack against the plant. Recent work is beginning to identify the mechanistic basis of these variable defences and how they are shaped by a plant's environment and correspondingly shape the plant's evolution. In this review, a number of these loci and their associated inferences are presented.
Costs of Resistance in Plants: From Theory to Evidence
Authors: Cipollini Don , Walters Dale , Voelckel Claudia
Published: May 2017

Plants defend themselves against attack by herbivores with a variety of physical and chemical defences, some of which also work by recruiting partners from the third trophic level. Despite the known or potential benefits of possessing defence traits, the expression of defence traits varies among tissues within individual plants, within and among plant populations, and across biotic and abiotic environments. The central explanation for such variation is that the expression of defence traits is costly to fitness in the absence of benefits. Here, we review how cost‐benefit trade‐offs have been incorporated in several hypotheses about the ecology and evolution of plant defences. We then describe several approaches that have been used to examine costs, and the empirical evidence that has been attained through their use. After 30 years of study, a consensus has emerged through a variety of approaches that expression of defence traits is, indeed, costly, but that the magnitude and importance of costs are context‐dependent.
Revisiting Plant‐Herbivore Co‐Evolution in the Molecular Biology Era
Authors: Jander Georg
Published: May 2017

Important theories that define the role of secondary metabolites in the co‐evolution of plants and insect herbivores were proposed in a series of publications in the 1950s and 1960s. Now, roughly 50 years later, it is possible to revisit these early theories and determine how well they hold up in the light of sequenced genomes, molecular phylogenies, completely elucidated biosynthetic pathways and evidence for specific biochemical detoxification mechanisms in insect herbivores. Two classes of plant secondary metabolites stand out as being particularly well‐studied: the glucosinolates, which are characteristic of cruciferous plants; and the benzoxazinoids, which are found in many grass species. Using these metabolic pathways as examples, it is possible to demonstrate at the molecular level how biosynthesis of plant secondary metabolites evolved from primary metabolism, how the development of defensive chemicals can drive plant‐herbivore co‐evolution and how insects are able to respond to plant defences at the molecular level.
Female undergraduate's perceptions of intrusive behavior in 12 countries
Authors: Sheridan Lorraine , Scott Adrian J. , Archer John , Roberts Karl
Published: May 2017

The present study examines young women's (N = 1,734) perceptions of the unacceptability of 47 intrusive activities enacted by men. Female undergraduate psychology students from 12 countries (Armenia, Australia, England, Egypt, Finland, India, Indonesia, Italy, Japan, Portugal, Scotland, Trinidad) indicated which of 47 intrusive activities they considered to be unacceptable. Responses were compared with parasite‐stress values, a measure of global gender equality and Hofstede's dimensions of national cultures. There was no unanimous agreement on any of the items, even for those relating to forced sexual violence. Cluster analysis yielded four clusters: “Aggression and surveillance” (most agreement that the constituent items were unacceptable), “Unwanted attention,” “Persistent courtship and impositions,” and “Courtship and information seeking” (least agreement that the constituent items were unacceptable). There were no significant relationships between the “Aggression and surveillance” or “Courtship and information seeking” clusters and the measure of gender equality, Hofstede's dimensions of national cultures or the measure of parasite stress. For the “Unwanted attention” and “Persistent courtship and impositions” clusters, women residing in countries with higher gender inequality and higher parasite‐stress were less accepting of behavior associated with uncommitted sexual relations, and women in more individualistic societies with higher levels of gender equality were less accepting of monitoring activities. Culture may take precedence over personal interpretations of the unacceptability of intrusive behavior that is not obviously harmful or benign in nature.
Evaluation of initial setup errors of two immobilization devices for lung stereotactic body radiation therapy (SBRT)
Authors: Ueda Yoshihiro , Teshima Teruki , Cárdenes Higinia , Das Indra J.
Published: May 2017

The aim of this study was to investigate the accuracy and efficacy of two commonly used commercial immobilization systems for stereotactic body radiation therapy (SBRT) in lung cancer. This retrospective study assessed the efficacy and setup accuracy of two immobilization systems: the Elekta Body Frame (EBF) and the Civco Body Pro‐Lok (CBP) in 80 patients evenly divided for each system. A cone beam CT (CBCT) was used before each treatment fraction for setup correction in both devices. Analyzed shifts were applied for setup correction and CBCT was repeated. If a large shift (>5 mm) occurred in any direction, an additional CBCT was employed for verification after localization. The efficacy of patient setup was analyzed for 105 sessions (48 with the EBF, 57 with the CBP). Result indicates that the CBCT was repeated at the 1st treatment session in 22.5% and 47.5% of the EBF and CBP cases, respectively. The systematic errors {left–right (LR), anterior–posterior (AP), cranio‐caudal (CC), and 3D vector shift: (LR2 + AP2 + CC2)1/2 (mm)}, were {0.5 ± 3.7, 2.3 ± 2.5, 0.7 ± 3.5, 7.1 ± 3.1} mm and {0.4 ± 3.6, 0.7 ± 4.0, 0.0 ± 5.5, 9.2 ± 4.2} mm, and the random setup errors were {5.1, 3.0, 3.5, 3.9} mm and {4.6, 4.8, 5.4, 5.3} mm for the EBF and the CBP, respectively. The 3D vector shift was significantly larger for the CBP (P < 0.01). The setup time was slightly longer for the EBF (EBF: 15.1 min, CBP: 13.7 min), but the difference was not statistically significant. It is concluded that adequate accuracy in SBRT can be achieved with either system if image guidance is used. However, patient comfort could dictate the use of CBP system with slightly reduced accuracy.
Understanding the Capacitance of PEDOT:PSS
Authors: Volkov Anton V. , Wijeratne Kosala , Mitraka Evangelia , Ail Ujwala , Zhao Dan , Tybrandt Klas , Andreasen Jens Wenzel , Berggren Magnus , Crispin Xavier , Zozoulenko Igor V.
Published: May 2017

Poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is the most studied and explored mixed ion‐electron conducting polymer system. PEDOT:PSS is commonly included as an electroactive conductor in various organic devices, e.g., supercapacitors, displays, transistors, and energy‐converters. In spite of its long‐term use as a material for storage and transport of charges, the fundamentals of its bulk capacitance remain poorly understood. Generally, charge storage in supercapacitors is due to formation of electrical double layers or redox reactions, and it is widely accepted that PEDOT:PSS belongs to the latter category. Herein, experimental evidence and theoretical modeling results are reported that significantly depart from this commonly accepted picture. By applying a two‐phase, 2D modeling approach it is demonstrated that the major contribution to the capacitance of the two‐phase PEDOT:PSS originates from electrical double layers formed along the interfaces between nanoscaled PEDOT‐rich and PSS‐rich interconnected grains that comprises two phases of the bulk of PEDOT:PSS. This new insight paves a way for designing materials and devices, based on mixed ion‐electron conductors, with improved performance.
Improved Performance and Stability of All‐Inorganic Perovskite Light‐Emitting Diodes by Antisolvent Vapor Treatment
Authors: Wu Chen , Zou Yatao , Wu Tian , Ban Muyang , Pecunia Vincenzo , Han Yujie , Liu Qipeng , Song Tao , Duhm Steffen , Sun Baoquan
Published: May 2017

All‐inorganic perovskite light‐emitting diodes (LEDs) reveal efficient luminescence with high color purity, but their modest brightness and poor stability are still critical drawbacks. Here, the luminescent efficiency and the stability of perovskite LEDs (PeLEDs) are boosted by antisolvent vapor treatment of CsPbBr3 embedded in a dielectric polymer matrix of polyethylene oxide (PEO). A unique method is developed to obtain high quality CsPbBr3 emitting layers with low defects by controlling their grain sizes. CsPbBr3 in PEO matrix is post‐treated with antisolvent of chloroform (CF), leading to microcrystals with a size of ≈5 µm along the in‐plane direction with active emitting composite of 90%. A device based on CF post‐treatment (CsPbBr3‐PEO‐CF) film displays a brightness of up to 51890 cd m−2 with an external quantum efficiency of 4.76%. CsPbBr3‐PEO‐CF PeLED still maintains 82% of its initial efficiency after 80 h continuous operation in ambient air, which indicates relatively good device stability. This work highlights that film quality is not only key to promoting fluorescence in CsPbBr3, but also to achieving higher performance PeLEDs.
Broad Spectrum Macromolecular Antimicrobials with Biofilm Disruption Capability and In Vivo Efficacy
Authors: Tan Jeremy P. K. , Coady Daniel J. , Sardon Haritz , Yuen Alexander , Gao Shujun , Lim Shaun W. , Liang Zhen Chang , Tan Eddy W. , Venkataraman Shrinivas , Engler Amanda C. , Fevre Mareva , Ono Robert , Yang Yi Yan , Hedrick James L.
Published: May 2017

In this study, antimicrobial polymers are synthesized by the organocatalytic ring‐opening polymerization of an eight‐membered heterocyclic carbonate monomer that is subsequently quaternized with methyl iodide. These polymers demonstrate activity against clinically relevant Gram‐positive Staphylococcus epidermidis and Staphylococcus aureus, Gram‐negative Escherichia coli and Pseudomonas aeruginosa, and fungus Candida albicans with fast killing kinetics. Importantly, the polymer efficiently inhibits biofilm growth and lyses existing biofilm, leading to a reduction in biomass and cell viability. In addition, the macromolecular antimicrobial is less likely to induce resistance as it acts via a membrane‐lytic mechanism. The polymer is not cytotoxic toward mammalian cells with LD50 of 99.0 ± 11.6 mg kg−1 in mice through i.v. injection. In an S. aureus blood stream infection mouse model, the polymer removes bacteria from the blood more rapidly than the antibiotic Augmentin. At the effective dose, the polymer treatment does not damage liver and kidney tissues or functions. In addition, blood electrolyte balance remains unchanged after the treatment. The low cost of starting materials, ease of synthesis, nontoxicity, broad spectrum activity with fast killing kinetics, and in vivo antimicrobial activity make these macromolecular antimicrobials ideal candidates for prevention of sepsis and treatment of infections.
Highly Luminescent Folate‐Functionalized Au22 Nanoclusters for Bioimaging
Authors: Pyo Kyunglim , Ly Nguyen Hoang , Yoon Sook Young , Shen Yiming , Choi Seon Young , Lee So Yeong , Joo Sang‐Woo , Lee Dongil
Published: May 2017

Gold nanoclusters are emerging as new materials for biomedical applications because of promises offered by their ultrasmall size and excellent biocompatibility. Here, the synthesis and optical and biological characterizations of a highly luminescent folate‐functionalized Au22 cluster (Au22‐FA) are reported. The Au22‐FA clusters are synthesized by functionalizing the surface of Au22(SG)18 clusters, where SG is glutathione, with benzyl chloroformate and folate. The functionalized clusters are highly water‐soluble and exhibit remarkably bright luminescence with a quantum yield of 42%, significantly higher than any other water‐soluble gold clusters protected with thiolate ligands. The folate groups conjugated to the gold cluster give rise to additional luminescence enhancement by energy transfer sensitization. The brightness of Au22‐FA is found to be 4.77 mM−1 cm−1, nearly 8‐fold brighter than that of Au22(SG)18. Further biological characterizations have revealed that the Au22‐FA clusters are well‐suited for bioimaging. The Au22‐FA clusters exhibit excellent photostability and low toxicity; nearly 80% cell viability at 1000 ppm of the cluster. Additionally, the Au22‐FA clusters show target specificity to folate‐receptor positive cells. Finally, the time‐course in vivo luminescence images of intravenous‐injected mice show that the Au22‐FA clusters are renal‐clearable, leaving only 8% of them remained in the body after 24 h post‐injection.
Vapor Phase Fabrication of Nanoheterostructures Based on ZnO for Photoelectrochemical Water Splitting
Authors: Barreca Davide , Carraro Giorgio , Gasparotto Alberto , Maccato Chiara , Altantzis Thomas , Sada Cinzia , Kaunisto Kimmo , Ruoko Tero‐Petri , Bals Sara
Published: May 2017

Nanoheterostructures based on metal oxide semiconductors have emerged as promising materials for the conversion of sunlight into chemical energy. In the present study, ZnO‐based nanocomposites have been developed by a hybrid vapor phase route, consisting in the chemical vapor deposition of ZnO systems on fluorine‐doped tin oxide substrates, followed by the functionalization with Fe2O3 or WO3via radio frequency‐sputtering. The target systems are subjected to thermal treatment in air both prior and after sputtering, and their properties, including structure, chemical composition, morphology, and optical absorption, are investigated by a variety of characterization methods. The obtained results evidence the formation of highly porous ZnO nanocrystal arrays, conformally covered by an ultrathin Fe2O3 or WO3 overlayer. Photocurrent density measurements for solar‐triggered water splitting reveal in both cases a performance improvement with respect to bare zinc oxide, that is mainly traced back to an enhanced separation of photogenerated charge carriers thanks to the intimate contact between the two oxides. This achievement can be regarded as a valuable result in view of future optimization of similar nanoheterostructured photoanodes.
MAP3K1‐related gonadal dysgenesis: Six new cases and review of the literature
Authors: Granados Andrea , Alaniz Veronica I. , Mohnach Lauren , Barseghyan Hayk , Vilain Eric , Ostrer Harry , Quint Elisabeth H. , Chen Ming , Keegan Catherine E.
Published: May 2017

Investigation of disorders of sex development (DSD) has resulted in the discovery of multiple sex‐determining genes. MAP3K1 encodes a signal transduction regulator in the sex determination pathway and is emerging as one of the more common genes responsible for 46,XY DSD presenting as complete or partial gonadal dysgenesis. Clinical assessment, endocrine evaluation, and genetic analysis were performed in six individuals from four unrelated families with 46,XY DSD. All six individuals were found to have likely pathogenic MAP3K1 variants. Three of these individuals presented with complete gonadal dysgenesis, characterized by bilateral streak gonads with typical internal and external female genitalia, while the other three presented with partial gonadal dysgenesis, characterized by incomplete testicular development, resulting in clitoral hypertrophy with otherwise typical female external genitalia. Testing for MAP3K1 variants should be considered in patients with 46,XY complete or partial gonadal dysgenesis, particularly in families with multiple members affected with 46,XY DSD. Identification of a MAP3K1 variant should prompt an evaluation for DSD in female siblings of the proband.
Drug‐induced anaphylaxis in the emergency room
Authors: Takazawa Tomonori , Oshima Kiyohiro , Saito Shigeru
Published: May 2017

Anaphylaxis is a life‐threatening, systemic allergic reaction that presents unique challenges for emergency care practitioners. Anaphylaxis occurs more frequently than previously believed. Therefore, proper knowledge regarding the epidemiology, mechanisms, symptoms, diagnosis, and treatment of anaphylaxis is essential. In particular, the initial treatment strategy, followed by correct diagnosis, in the emergency room is critical for preventing fatal anaphylaxis, although making a diagnosis is not easy because of the broad and often atypical presentation of anaphylaxis. To this end, the clinical criteria proposed by the National Institute of Allergy and Infectious Diseases and the Food Allergy and Anaphylaxis Network are useful, which, together with a differential diagnosis, could enable a more accurate diagnosis. Additional in vitro tests, such as plasma histamine and tryptase measurements, are also helpful. It should be emphasized that adrenaline is the only drug recommended as first‐line therapy in all published national anaphylaxis guidelines. Most international anaphylaxis guidelines recommend injecting adrenaline by the intramuscular route in the mid‐anterolateral thigh, whereas i.v. adrenaline is an option for patients with severe hypotension or cardiac arrest unresponsive to intramuscular adrenaline and fluid resuscitation. In addition to the route of administration, choosing the appropriate dose of adrenaline is essential, because serious adverse effects can potentially occur after an overdose of adrenaline. Furthermore, to avoid future recurrence of anaphylaxis, providing adrenaline auto‐injectors and making an etiological diagnosis, including confirmation of the offending trigger, are recommended for patients at risk of anaphylaxis before their discharge from the emergency room.
Theory of invariants‐based formulation of Hamiltonians with application to strained zinc‐blende crystals
Authors: Wanner Johannes , Eckern Ulrich , Höck Karl‐Heinz
Published: May 2017

Group theoretical methods and theory are combined to determine spin‐dependent contributions to the effective conduction band Hamiltonian. To obtain the constants in the effective Hamiltonian, in general all invariants of the Hamiltonian have to be determined. Hence, we present a systematic approach to keep track of all possible invariants and apply it to the Hamiltonian of crystals with zinc‐blende symmetry, in order to find all possible contributions to effective quantities such as effective mass, g‐factor and Dresselhaus constant. Additional spin‐dependent contributions to the effective Hamiltonian arise in the presence of strain. In particular, with regard to the constants C3 and D which describe spin‐splitting linear in the components of k and ε, considering all possible terms allowed by symmetry is crucial.
The ergodic side of the many‐body localization transition
Authors: Luitz David J. , Lev Yevgeny Bar
Published: May 2017

Recent studies point towards nontriviality of the ergodic phase in systems exhibiting many‐body localization (MBL), which shows subexponential relaxation of local observables, subdiffusive transport and sublinear spreading of the entanglement entropy. Here we review the dynamical properties of this phase and the available numerically exact and approximate methods for its study. We discuss in which sense this phase could be considered ergodic and present possible phenomenological explanations of its dynamical properties. We close by analyzing to which extent the proposed explanations were verified by numerical studies and present the open questions in this field.

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Asymmetric Copper‐Catalyzed Carbomagnesiation of Cyclopropenes
Authors: Dian Longyang , Müller Daniel S. , Marek Ilan
Published: May 2017

The highly diastereo‐ and enantioselective formation of polysubstituted cyclopropanes was easily achieved through the asymmetric copper‐catalyzed carbomagnesiation reaction of nonfunctionalized cyclopropene derivatives. The carbometalated species generated in situ readily undergo C−C and C−X bond‐forming reactions with various electrophiles with complete retention of configuration.
Eine einfache Methode der nachträglichen Modifizierung zur Kontrolle der Seitenketteninformation digitaler Polymere
Authors: König Niklas Felix , Al Ouahabi Abdelaziz , Poyer Salomé , Charles Laurence , Lutz Jean‐François
Published: May 2017

Für das Design informationstragender Polyphosphodiester mit kontrollierbar einzuführenden Seitenketten wurde eine dreistufige polymeranaloge Syntheseroute entwickelt. Durch Phosphoramidit‐Synthese wurden dazu entweder manuell auf Polystyrolharz oder automatisiert auf einer CPG‐Festphase Sequenzen mit definierter Primärstruktur als Vorstufe erhalten. Verwendet wurden dabei zwei Monomere, die terminale Alkine oder analog die mit Triisopropylsilyl (TIPS) geschützten Alkine als Substituenten aufweisen. Derlei Polymere sind dann stufenweise der Huisgen‐Reaktion (CuAAC) zugänglich. So wurden zuerst die terminalen Alkine mit einem Azid umgesetzt und nach Abspaltung der TIPS‐Gruppen konnten die dabei gebildeten terminalen Alkine mit einem weiteren Azid reagieren. Diese einfache Strategie gestattet die quantitative Modifizierung der Monomerseitenketten. Dies wiederum eröffnet den Zugang zu einer Vielzahl verschiedener digitaler Polymere.
From Discrete Molecular Cages to a Network of Cages Exhibiting Enhanced CO2 Adsorption Capacity
Authors: Zhang Lei , Xiang Long , Hang Cheng , Liu Wenlong , Huang Wei , Pan Yichang
Published: May 2017

We have adopted the concept of “cage to frameworks” to successfully produce a Na–N connected coordination networked cage Na‐NC1 by using a [3+6] porous imine‐linked organic cage NC1 (Nanjing Cage 1) as the precursor. It is found that Na‐NC1 exhibits hierarchical porosity (inherent permanent voids and interconnected channel) and gas sorption measurements reveal a significantly enhanced CO2 uptake (1093 cm3 g−1 at 23 bar and 273 K) than that of NC1 (162 cm3 g−1 under the same conditions). In addition, Na‐NC1 exhibits very low CO2 adsorption enthalpy making it a good candidate for porous materials with both high CO2 storage and low adsorption enthalpy.
Plasmonic‐Based Electrochemical Impedance Imaging of Electrical Activities in Single Cells
Authors: Liu Xian‐Wei , Yang Yunze , Wang Wei , Wang Shaopeng , Gao Ming , Wu Jie , Tao Nongjian
Published: May 2017

Studying electrical activities in cells, such as action potential and its propagation in neurons, requires a sensitive and non‐invasive analytical tool that can image local electrical signals with high spatial and temporal resolutions. Here we report a plasmonic‐based electrochemical impedance imaging technique to study transient electrical activities in single cells. The technique is based on the conversion of the electrical signal into a plasmonic signal, which is imaged optically without labels. We demonstrate imaging of the fast initiation and propagation of action potential within single neurons, and validate the imaging technique with the traditional patch clamp technique. We anticipate that the plasmonic imaging technique will contribute to the study of electrical activities in various cellular processes.
Planarchirale Aminosiloxide
Authors: Golz Christopher , Steffen Patricia , Strohmann Carsten
Published: May 2017

Die Synthese, Struktur und exemplarische Reaktivität von Siloxiden mit planarchiralem N,N‐Dimethylaminomethylferrocen‐Rückgrat wird vorgestellt. Mehrere Zinkkomplexe ausgehend aus dem racemischen als auch dem enantiomerenreinen Silanol wurden in Gegenwart von Wasser synthetisiert, kristallographisch charakterisiert und auf ihr Verhalten in Lösung untersucht. Die in diesem System vorhandene chirale Sonde stellt sich als wertvolles Werkzeug zur Identifizierung der vorliegenden Struktur in Lösung heraus. Weiterhin zeigen die Zinksiloxide eine vergleichbare Reaktivität wie die entsprechenden Silanole. Daher bieten sich diese als “maskierte” Silanole an, vor allem dann, wenn die Silanole präparativ unzugänglich sind.
Lanthanide Metal–Organic Framework Microrods: Colored Optical Waveguides and Chiral Polarized Emission
Authors: Yang Xiaogang , Lin Xianqing , Zhao Yibing , Zhao Yong Sheng , Yan Dongpeng
Published: May 2017

Lanthanide metal–organic frameworks (Ln‐MOFs) have received much attention owing to their structural tunability and widely photofunctional applications. However, successful examples of Ln‐MOFs with well‐defined photonic performances at micro‐/nanometer size are still quite limited. Herein, self‐assemblies of 1,3,5‐benzenetricarboxylic acid (BTC) and lanthanide ions afford isostructural crystalline Ln‐MOFs. Tb‐BTC, Eu@Tb‐BTC, and Eu‐BTC have 1D microrod morphologies, high photoluminescence (PL) quantum yields, and different emission colors (green, orange, and red). Spatially PL resolved spectra confirm that Ln‐MOF microrods exhibit an optical waveguide effect with low waveguide loss coefficient (0.012≈0.033 dB μm−1) during propagation. Furthermore, these microrods feature both linear and chiral polarized photoemission with high anisotropy.
Synthesis and antimicrobial activity of bulky 3,5‐di‐tert‐butyl substituent‐containing silver–N‐heterocyclic carbene complexes
Authors: Kaloğlu Nazan , Özdemir İlknur , Günal Selami , Özdemir İsmail
Published: May 2017

A series of novel benzimidazolium bromides containing bulky 3,5‐di‐tert‐butyl group were synthesized in high yields as N‐heterocyclic carbene (NHC) ligands. These NHC ligands were metallated with Ag2O under moderate conditions to give novel silver–NHC complexes. The structures of all compounds were characterized using 1H NMR, 13CNMR, infrared and elemental analysis techniques, which supported the proposed structures. The silver–NHC complexes were screened for their in vitro antimicrobial activities against the standard bacterial strains Enterococcus faecalis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa and the fungal strains Candida albicans and C. tropicalis. The results showed that most of the silver–NHC complexes inhibited the growth of all bacterial strains and fungal strains and were found to display effective antimicrobial activity against different microorganisms.
Destruction of chitosan capsules based on host–guest interaction and controllable release of encapsulated dyes
Authors: Shang Chunyang , Chen Yanjun , Zhang Chaocan , Deng Zongyi , Wu Zhihui
Published: May 2017

This article describes a new and simple method to control the release of payloads encapsulated in chitosan capsules. The capsules with the liquid core and rigid shell are performed by drop‐wisely adding chitosan solution into anionic surfactant solution. The capsules can be destroyed by β‐CD because β‐CD binds and sequesters surfactant from the shell through the host‐guest interaction. The destruction process is studied by optical microscopy and scanning electron microscopy. The capsules can swell in acid solution and shrink in alkaline solution. It is found that the destruction speed increases with increasing acidity or alkalinity of β‐CD solution. Rhodamine B encapsulated in the liquid‐core of chitosan capsules can be released from the capsules in β‐CD solution. The release rate can be adjusted by the pH value of β‐CD solution. The release speed of the capsule increases with the increase of acidity or alkalinity in β‐CD solution. The above concept can provide more versatility for controlled release of a variety of payloads such as drugs, cosmetics, and so on. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45229.
Polysiloxane/polyacrylate composite latexes with balanced mechanical property and breathability: Effect of core/shell mass ratio
Authors: Shen Jie , Sun Jian‐wu , Hu Yang , Kan Cheng‐you
Published: May 2017

Polysiloxane/polyacrylate (PSi/PA) core/shell latexes are fabricated, and the particle morphology, the film structure, as well as the properties of the latex films are investigated by comparing with blend latexes, and the relationship between structure and property is proposed. Results indicate that the structure and property of the latex films heavily depend on the particle morphology. The sea–island latex films with uniform distribution of PSi phases can be formed from the PSi/PA core/shell latexes, and with the mass ratio from 1:1 to 1:4, their tensile strength and elongation at break are close to the pure PA latex film, while the elastic recovery and water vapor permeability improve notably. It is found that the phase segregation occurs in the blend latex films, and although the blend latex films provide better water vapor breathability, their mechanical properties sacrifice obviously. Therefore, the various properties must be balanced for practical applications and the core/shell latexes are competitive for meeting the balanced requirements. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45258.
Pyrazolo[4,3‐h]quinoline Ligand‐Based Iridium(III) Complexes for Electrochemiluminescence
Authors: Hsu Chien‐Wei , Longhi Elena , Sinn Stephan , Hawes Chris S. , Young David C. , Kruger Paul E. , Cola Luisa De
Published: May 2017

Electrochemiluminescence (ECL) based on [Ru(bpy)3]2+ systems is widely utilized for immunoassays. In order to extend the promising potential of ECL‐based applications, IrIII complexes have recently attracted attention as probes because of their excellent luminescent properties and tunable emission wavelength. Here we describe a series of Ir complexes using a large π‐conjugated ligand and different ancillary chelates. The complexes synthesized have been chemically and spectroscopically characterized and used for ECL measurements with annihilation and co‐reactant methods. One of the IrIII complexes investigated exhibits the brightest, ever reported, ECL efficiency in acetonitrile employing the benzoyl peroxide (BPO) co‐reactant method.
Grundlegende Untersuchungen zur Überarbeitung der Muster‐Industriebaurichtlinie
Authors: Kruse Dirk , Zobel Andre
Published: May 2017

Im Rahmen eines Forschungsprojekts sollen Grundlagen für eine stärkere Verwendung von Holzbauweisen bei Industriebauten geschaffen werden. Dazu wurden aus der Holzbranche die wesentlichen Hemmnisse identifiziert. Mittels einer Analyse von gebauten Beispielen wurde untersucht, in welchem Umfang eine (brennbare) Holzkonstruktion überhaupt einen Einfluss auf das zu erwartende Brandszenario hat. Die Hallen wurden dazu hinsichtlich ihrer Nutzungen und der vorhandenen Brandlasten im Detail untersucht. Aus den Ergebnissen sollen Vorschläge zur Überarbeitung der Muster‐Holzbaurichtlinie abgeleitet werden.
Genetic vulnerabilities to prenatal alcohol exposure: Limb defects in sonic hedgehog and GLI2 heterozygous mice
Authors: Fish Eric W. , Murdaugh Laura B. , Sulik Kathleen K. , Williams Kevin P. , Parnell Scott E.
Published: May 2017

Background

Genetic factors influence the physical and neurobehavioral manifestations of prenatal alcohol exposure (PAE). Animal models allow the investigation of specific genes that confer vulnerability to, or protection from, birth defects associated with fetal alcohol spectrum disorders (FASDs). The objective of the present experiments was to determine if genetic alterations in the Sonic Hedgehog (Shh) signaling pathways affect the vulnerability to PAE‐induced skeletal defects involving the forelimbs and/or hindlimbs.

Method

Wild‐type C57BL/6J female mice were bred with males in which one copy of the Shh or Gli2 genes had been knocked out, to produce litters with both wild‐type (+/+) and heterozygous (+/−) embryos. Alcohol doses (two injections of 2.9 g/kg, 4 hours apart) or vehicles were administered starting at gestational day (GD) 9.25, 9.5, or 9.75, a critical exposure time for inducing limb defects. Limb defects were examined at GD 17 using a dysmorphology scale based on abnormalities ranging from increased interdigital spacing to the deletion of multiple fingers and the ulna.

Results

Alcohol treatment caused a high incidence of forelimb defects, particularly on the right side, that was higher in Shh+/− and Gli2+/− fetuses compared to wild‐type fetuses. Dysmorphology scores were also significantly higher in the Shh+/− and Gli2+/− mice.

Conclusions

These results extend previous findings demonstrating enhanced sensitivity to PAE‐induced craniofacial dysmorphology and support the hypothesis that genetic alterations in the Shh signaling pathway influences the vulnerability to alcohol‐induced birth defects. Moreover, these results emphasize the importance of understanding the interactions between genes and prenatal exposure to alcohol or other teratogens. Birth Defects Research 109:860–865, 2017. © 2017 Wiley Periodicals, Inc.
Modelling adult skills in OECD countries
Authors: Scandurra Rosario , Calero Jorge
Published: May 2017

Research in the social sciences has focused extensively on the relationship between family background, educational attainment and social destination, on the one hand, and on the processes of skills creation and skills use, on the other. This paper brings these two branches of the literature together by examining the correlation between a range of social factors. The methodology we adopt provides a comprehensive approach to the study of the channels through which literacy skills are acquired, taking into account the interrelation of family background, educational attainment, and the use of skills at work and at home. We use the Programme of International Assessment of Adult Competences (PIAAC) dataset and apply a structural equation model (SEM). Our results show that family background and education play an important role in the configuration of adult skills and skill practices. Unequal family access to resources has a strong impact at later stages in life and strongly affects educational attainment and skills outcomes. Additionally, skills use has a positive and direct impact on adult skills.
Electronic and Ligand Properties of Skeletally Substituted Cyclic (Alkyl)(Amino)Carbenes (CAACs) and Their Reactivity towards Small Molecule Activation: A Theoretical Study
Authors: Bharadwaz Priyam , Chetia Pubali , Phukan Ashwini K.
Published: May 2017

Quantum chemical calculations have been carried out to understand the ligand properties of skeletally modified cyclic alkyl amino carbenes. The stability of these carbenes has been assessed from an evaluation of their singlet–triplet and stabilization energy values. Ylide substituted carbenes are found to be more stable than non‐ylidic ones in their optimized singlet state. Nucleophilicity and electrophilicity indices values were evaluated in order to further investigate the reactivity of these carbenes. The calculated values of proton affinities and the degree of gallium pyramidalization in the carbene‐GaCl3 adducts correlate well with the σ‐basicity of these carbenes. The reactivity of non‐ylidic carbenes toward the activation of both H2 and NH3 are calculated to be more favourable compared to that of parent CAAC. On the other hand, ylide anchored carbenes are found to be unsuccessful toward the activation of both H2 and NH3.
Hydrogenation of Carbon Dioxide to Methanol Catalyzed by Iron, Cobalt, and Manganese Cyclopentadienone Complexes: Mechanistic Insights and Computational Design
Authors: Ge Hongyu , Chen Xiangyang , Yang Xinzheng
Published: May 2017

Invited for the cover of this issue is the group of Xinzhen Yang at Institute of Chemistry, Chinese Academy of Sciences. The image depicts a series of computationally designed iron, cobalt, and manganese cyclopentadienone catalysts for hydrogenation of carbon dioxide to methanol. Read the full text of the article at 10.1002/chem.201701200.
Design, Synthesis, and Structure–Activity Relationship Analysis of Thiazolo[3,2‐a]pyrimidine Derivatives with Anti‐inflammatory Activity in Acute Lung Injury
Authors: Chen Lingfeng , Jin Yiyi , Fu Weitao , Xiao Siyang , Feng Chen , Fang Bo , Gu Yugui , Li Chenglong , Zhao Yunjie , Liu Zhiguo , Liang Guang
Published: May 2017

Acute lung injury (ALI) has a high lethality rate, and interleukin‐6 (IL‐6) and tumor necrosis factor‐α (TNF‐α) contribute most to tissue deterioration in cases of ALI. In this study, we designed and synthesized a new series of thiazolo[3,2‐a]pyrimidine derivatives based on a previously identified lead compound, and we evaluated their anti‐inflammatory activities. Structure–activity relationship studies led to the discovery of two highly potent inhibitors. The two promising compounds were found to inhibit lipopolysaccharide (LPS)‐induced IL‐6 and TNF‐α release in a dose‐dependent manner in mouse primary peritoneal macrophages (MPMs). Furthermore, administration of these compounds resulted in lung histopathological improvements and attenuated LPS‐induced ALI in vivo. Taken together, these data indicate that these novel thiazolo[3,2‐a]pyrimidine derivatives could be developed as candidate drugs for the treatment of ALI.
1,2,4‐Triazole‐3‐thione Compounds as Inhibitors of Dizinc Metallo‐β‐lactamases
Authors: Sevaille Laurent , Gavara Laurent , Bebrone Carine , De Luca Filomena , Nauton Lionel , Achard Maud , Mercuri Paola , Tanfoni Silvia , Borgianni Luisa , Guyon Carole , Lonjon Pauline , Turan‐Zitouni Gülhan , Dzieciolowski Julia , Becker Katja , Bénard Lionel , Condon Ciaran , Maillard Ludovic , Martinez Jean , Frère Jean‐Marie , Dideberg Otto , Galleni Moreno , Docquier Jean‐Denis , Hernandez Jean‐François
Published: May 2017

Metallo‐β‐lactamases (MBLs) cause resistance of Gram‐negative bacteria to β‐lactam antibiotics and are of serious concern, because they can inactivate the last‐resort carbapenems and because MBL inhibitors of clinical value are still lacking. We previously identified the original binding mode of 4‐amino‐2,4‐dihydro‐5‐(2‐methylphenyl)‐3H‐1,2,4‐triazole‐3‐thione (compound IIIA) within the dizinc active site of the L1 MBL. Herein we present the crystallographic structure of a complex of L1 with the corresponding non‐amino compound IIIB (1,2‐dihydro‐5‐(2‐methylphenyl)‐3H‐1,2,4‐triazole‐3‐thione). Unexpectedly, the binding mode of IIIB was similar but reverse to that of IIIA. The 3 D structures suggested that the triazole–thione scaffold was suitable to bind to the catalytic site of dizinc metalloenzymes. On the basis of these results, we synthesized 54 analogues of IIIA or IIIB. Nineteen showed IC50 values in the micromolar range toward at least one of five representative MBLs (i.e., L1, VIM‐4, VIM‐2, NDM‐1, and IMP‐1). Five of these exhibited a significant inhibition of at least four enzymes, including NDM‐1, VIM‐2, and IMP‐1. Active compounds mainly featured either halogen or bulky bicyclic aryl substituents. Finally, some compounds were also tested on several microbial dinuclear zinc‐dependent hydrolases belonging to the MBL‐fold superfamily (i.e., endonucleases and glyoxalase II) to explore their activity toward structurally similar but functionally distinct enzymes. Whereas the bacterial tRNases were not inhibited, the best IC50 values toward plasmodial glyoxalase II were in the 10 μm range.
Mechanical and Drug Release Properties of Sponges from Cross‐linked Cellulose Nanofibers
Authors: Fiorati Andrea , Turco Gianluca , Travan Andrea , Caneva Enrico , Pastori Nadia , Cametti Massimo , Punta Carlo , Melone Lucio
Published: May 2017

All‐organic porous sponges were obtained throughout the direct and solvent‐free (oven 105 °C, time>6 h) crosslinking of TEMPO‐oxidized cellulose nanofibers (TOCNF) with 25 kDa branched polyethyleneimine (bPEI) in the presence of different amounts of citric acid (CA) as co‐crosslinker. The chemical and mechanical stability of these materials was provided by the formation of amide bonds between the carboxylic moieties of TOCNF and CA with the primary amines of bPEI. The mechanical properties were investigated under static and dynamic loads with both dry and wet samples. The materials had the interesting capability to recover their shape with reduced losses in mechanical resistance, while their Young's modulus progressively increased with the content of CA. In work toward developing possible applications of bPEI‐TOCNF sponges in drug delivery, amoxicillin (AM) and ibuprofen (IB) were considered as model drugs. All materials showed very good performance in adsorbing both AM and IB (ca. 200 mg g−1) from methanol solution. In particular, an increased adsorption of IB was observed in parallel to the increase of citrate moieties in the samples. Moreover, samples crosslinked in presence of CA showed slower kinetic release in aqueous environments than materials obtained without CA.
Synthesis of 3‐Benzylated Isoindolinones by Photoredox Decarboxylation of Arylacetates in the Presence of N‐Benzylphthalimide: Conductivity as a Kinetic Tool
Authors: Griesbeck Axel G. , Neudörfl Jörg.‐M. , Goldfuss Bernd , Molitor Sabrina
Published: May 2017

N‐Benzylphthalimide was selectively monobenzylated when irradiated in the presence of arylacetates in aqueous solution with acetone acting as the triplet sensitizer. The resulting 3‐hydroxyisoindolinones were dehydrated to the corresponding alkenes and hydrogenated to give 3‐benzylisoindolinones, overall a straight‐forward route to biologically relevant isoindolinone structures. Following kinetic traces by conductivity measurements revealed that the primary electron transfer is rate‐determining in contrast to acetate or other alkyl carboxylates as electron‐donor components.