bluuebunny/crossref_metadata_2025 huggingface dataset:
The Water‐Energy Nexus of Hydraulic Fracturing: A Global Hydrologic Analysis for Shale Oil and Gas Extraction
Authors: Rosa Lorenzo , Rulli Maria Cristina , Davis Kyle Frankel , D'Odorico Paolo
Published: April 2018

Shale deposits are globally abundant and widespread. Extraction of shale oil and shale gas is generally performed through water‐intensive hydraulic fracturing. Despite recent work on its environmental impacts, it remains unclear where and to what extent shale resource extraction could compete with other water needs. Here we consider the global distribution of known shale deposits suitable for oil and gas extraction and develop a water balance model to quantify their impacts on local water availability for other human uses and ecosystem functions. We find that 31–44% of the world's shale deposits are located in areas where water stress would either emerge or be exacerbated as a result of shale oil or gas extraction; 20% of shale deposits are in areas affected by groundwater depletion and 30% in irrigated land. In these regions shale oil and shale gas production would likely compete for local water resources with agriculture, environmental flows, and other water needs. By adopting a hydrologic perspective that considers water availability and demand together, decision makers and local communities can better understand the water and food security implications of shale resource development.
Response to Comment by Walker et al. on “From Data to Decisions: Processing Information, Biases, and Beliefs for Improved Management of Natural Resources and Environments”
Authors: Glynn Pierre D. , Voinov Alexey A. , Shapiro Carl D. , White Paul A.
Published: April 2018

Our different kinds of minds and types of thinking affect the ways we decide, take action, and cooperate (or not). The comment by Walker et al. (2018, https://doi.org/10.1002/2017EF000750) illustrates several points made by Glynn et al. (2017, https://doi.org/10.1002/2016EF000487) and many other articles. Namely, biases and beliefs often drive scientific reasoning, and scientists, just like other humans, are intimately attached to their values and heuristics. Scientists, just like many other people, also tend to read and interpret text in ways that best match their individual perceptions of a problem or issue: in many cases paraphrasing and changing the meaning of what they read to better match their initial ideas. Walker et al. are doing interesting and important research on uncertainty. Nonetheless, they misinterpret the work, assumptions, and conclusions brought forth by Glynn et al. (2017, https://doi.org/10.1002/2016EF000487).
Human Cell Encapsulation in Gel Microbeads with Cosynthesized Concentric Nanoporous Solid Shells
Authors: Zhou Xiamo Chianty , Haraldsson Tommy , Nania Salvatore , Ribet Federico , Palano Giorgia , Heuchel Rainer , Löhr Matthias , van der Wijngaart Wouter
Published: April 2018

Encapsulation of therapeutic cells in core–shell microparticles has great promise for the treatment of a range of health conditions. Unresolved challenges related to control of the particle morphology, mechanical stability, and immunogenicity hinder dissemination of this promising approach. Here, a novel polymer material for cell encapsulation and a combined novel, easy to control, synthesis method are introduced. Core–shell cell encapsulation is demonstrated with a concentric core–shell morphology formed during a single UV exposure, resulting in particles that consist of a synthetic hydrogel core of polyethylene glycol diacrylate and a solid, but porous, shell of off‐stoichiometric thiol‐ene. The encapsulated human cells in 100 µm diameter particles have >90% viability. The average shell thickness is controlled between 7 and 13 µm by varying the UV exposure, and the shell is measured to be permeable to low molecular weight species (<180 Da) but impermeable to higher molecular weight species (>480 Da). The unique material properties and the orthogonal control of the microparticle core size, shell thickness, shell permeability, and shell surface properties address the key unresolved challenges in the field, and are expected to enable faster translation of novel cell therapy concepts from research to clinical practice.
The Coral Protein CARP3 Acts from a Disordered Mineral Surface Film to Divert Aragonite Crystallization in Favor of Mg‐Calcite
Authors: Gavriel Rotem , Nadav‐Tsubery Merav , Glick Yehonatan , Yarmolenko Alina , Kofman Renana , Keinan‐Adamsky Keren , Berman Amir , Mass Tali , Goobes Gil
Published: April 2018

Stony corals construct their aragonite skeleton by calcium carbonate precipitation, in a process recently suggested to be biologically controlled. Amorphous calcium carbonate and small amounts of calcite are also reported recently, however, their functional role is unknown. Coral acid‐rich proteins (CARPs) are extracted from the coral skeleton and are shown to be active in calcium carbonate precipitation in vitro. However, individual function of these proteins in coral mineralization is not known. Here, the regulatory activity of the aspartate‐rich CARP3 protein is examined. The whole protein and two peptides representing its acidic domain and its variable domain are used in CaCO3 precipitation reactions from Mg‐rich solutions. The biomolecules alter crystallization pathways, promoting Mg‐calcite in place of aragonite, with the acidic peptide capable of eradicating aragonite formation. The activity of CARP3 and its representative peptides is exerted from disordered CaCO3 mineral phases, coating the crystals formed, as shown by 2D 1H–13C heteronuclear correlation nuclear magnetic resonance (NMR) measurements, localizing organic protons in atomic proximity to disordered carbonate carbons. The structures of the protein and individual domains as derived from NMR measurements and folding calculations and their amino acid compositions are discussed in the context of their observed activity and its implication to mineralization in hard corals.
Interlayer Coupling Induced Infrared Response in WS2/MoS2 Heterostructures Enhanced by Surface Plasmon Resonance
Authors: Wang Guichao , Li Liang , Fan Weihao , Wang Renyan , Zhou Shasha , Lü Jing‐Tao , Gan Lin , Zhai Tianyou
Published: April 2018

Infrared light detection is generally limited by the intrinsic bandgap of semiconductors, which suppresses the freedom in infrared light photodetector design and hinders the development of high‐performance infrared light photodetector. In this work, for the first time infrared light (1030 nm) photodetectors are fabricated based on WS2/MoS2 heterostructures. Individual WS2 and MoS2 have no response to infrared light. The origin of infrared light response for WS2/MoS2 comes from the strong interlayer coupling which shrinks the energy interval in the heterojunction area thus rendering heterostructures longer wavelength detection ability compared to individual components. Considering the low light absorption due to indirect bandgap essence of few layers WS2/MoS2 heterostructures, its infrared responsivity is further enhanced with at most ≈25 times but the fast response rate is maintained via surface plasmon resonance (SPR). Such an interlayer coupling induced infrared light response and surface plasmon resonance enhancement strategy paves the way for high‐performance infrared light photodetection of infinite freedom in design.
Wearable Superhydrophobic Elastomer Skin with Switchable Wettability
Authors: Wang Jian‐Nan , Liu Yu‐Qing , Zhang Yong‐Lai , Feng Jing , Wang Huan , Yu Yan‐Hao , Sun Hong‐Bo
Published: April 2018

Flexible smart surfaces with tunable wettability are promising for emerging wearable uses. However, currently, wearable superhydrophobic surfaces with dynamic wetting behaviors are rarely reported. Here, a skin‐like superhydrophobic elastomer surface with switchable lotus leaf and rose petal states is reported. Direct laser writing technique is employed for one‐step, programmable, large‐scale fabrication of monolithic and hierarchical micro‐nanostructures on elastomer, leading to strong water repellence. The surface topography can be finely regulated in a rapid and reversible manner by simple stretching, providing the feasibility of controlling the surface wettability by simple body motions. The ability to switch wetting states enables the surface to capture and release multiple droplets in parallel. Furthermore, the active surface can be applied to the joints of fingers and operate as a droplet manipulator under finger motions without requiring energy supply or external appliance. In this work, dynamic tuning of wetting properties is integrated into the design of skin‐like wearable surfaces, revealing great potential in versatile applications such as wearable droplet manipulator, portable actuator, adaptive adhesion control, liquid repellent skin, and smart clothing.
Phototunable Dielectric Huygens' Metasurfaces
Authors: Fan Kebin , Zhang Jingdi , Liu Xinyu , Zhang Gu‐Feng , Averitt Richard D. , Padilla Willie J.
Published: April 2018

Conventional dielectric metasurfaces achieve their properties through geometrical tuning and consequently are static. Although some unique properties are demonstrated, the usefulness for realistic applications is thus inherently limited. Here, control of the resonant eigenmodes supported by Huygens' metasurface (HMS) absorbers through optical excitation is proposed and demonstrated. An intensity transmission modulation depth of 99.93% is demonstrated at 1.03 THz, with an associated phase change of greater than π/2 rad. Coupled mode theory and S‐parameter simulations are used to elucidate the mechanism underlying the dynamics of the metasurface and it is found that the tuning is primarily governed by modification of the magnetic dipole‐like odd eigenmode, which both lifts the degeneracy, and eliminates critical coupling. The dynamic HMS demonstrates wide tunability and versatility which is not limited to the spectral range demonstrated, offering a new path for reconfigurable metasurface applications.
Elastic Self‐Doping Organic Single Crystals Exhibiting Flexible Optical Waveguide and Amplified Spontaneous Emission
Authors: Huang Rui , Wang Chenguang , Wang Yue , Zhang Hongyu
Published: April 2018

Organic crystals are generally brittle and tend to crack under applied stress. Doped organic crystals are even more brittle because of lattice defects. Herein, the first doped organic crystals 1d@2d, which display elastic bending ability under applied stress, are reported. Moreover, the potential applications of elastic‐doped crystals 1d@2d in flexible optoelectronics are impressively demonstrated. The elastic crystals 1d@2d with high quality and large size are crystalized by a simple and unique “self‐doping” process, which is a regular solution evaporation of crude product 1d (2,5‐dihydro‐3,6‐bis(octylamino)terephthalate) containing a minute amount of 2d (3,6‐bis(octylamino)terephthalate) as the oxidized byproduct. The host 1d is easily crystallized to form elastic crystals but is nonfluorescent, while the guest 2d has poor crystallinity and is highly emissive. The doping approach integrates the advantages of both 1d and 2d, and thus endows doped crystals 1d@2d with good elasticity as well as intense orange fluorescence. Taking these advantages, the application potentials of these doped crystals 1d@2d are evaluated by measuring optical waveguide and amplified spontaneous emission in both the straight and bent states.
Metal‐Free Artificial Photosynthesis of Carbon Monoxide Using N‐Doped ZnTe Nanorod Photocathode Decorated with N‐Doped Carbon Electrocatalyst Layer
Authors: Jang Youn Jeong , Bhatt Mahesh Datt , Lee Jaehyuk , Choi Sun Hee , Lee Byeong Jun , Lee Jae Sung
Published: April 2018

An artificial photosynthesis system based on N‐doped ZnTe nanorods decorated with an N‐doped carbon electrocatalyst layer is fabricated via an all‐solution process for the selective conversion of CO2 to CO. Substitutional N‐doping into the ZnTe lattice decreases the bandgap slightly and improves the charge transfer characteristics, leading to enhanced photoelectrochemical activity. Remarkable N‐doping effects are also demonstrated by the N‐doped carbon layer that promotes selective CO2‐to‐CO conversion instead of undesired water‐to‐H2 reduction by providing active sites for CO2 adsorption and activation, even in the absence of metallic redox centers. The photocathode shows promising performance in photocurrent generation (−1.21 mA cm−2 at −0.11 VRHE), CO selectivity (dominant CO production of ≈72%), minor H2 reduction (≈20%), and stability (corrosion suppression). The metal‐free electrocatalyst/photocatalyst combination prepared via a cost‐effective solution process exhibits high performance due to synergistic effects between them, and thus may find application in practical solar fuel production.
Modeling granular material blending in a rotating drum using a finite element method and advection‐diffusion equation multiscale model
Authors: Liu Yu , Gonzalez Marcial , Wassgren Carl
Published: April 2018

A multiscale model is presented for predicting the magnitude and rate of powder blending in a rotating drum blender. The model combines particle diffusion coefficient correlations from the literature with advective flow field information from blender finite element method simulations. The multiscale model predictions for overall mixing and local concentration variance closely match results from discrete element method (DEM) simulations for a rotating drum, but take only hours to compute as opposed to taking days of computation time for the DEM simulations. Parametric studies were performed using the multiscale model to investigate the influence of various parameters on mixing behavior. The multiscale model is expected to be more amenable to predicting mixing in complex geometries and scale more efficiently to industrial‐scale blenders than DEM simulations or analytical solutions. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3277–3292, 2018
Tumor necrosis factor‐alpha −1031T/C polymorphism is associated with cognitive deficits in chronic schizophrenia patients versus healthy controls
Authors: Xiu Mei Hong , Man Li‐Juan , Wang Dong , Du Xiangdong , Yin Guangzhou , Zhang Yingyang , Tan Yun Long , Chen Nan , Chen Song , Teixeira Antonio L. , Cassidy Ryan. M. , Soares Jair C. , Zhang Xiang Yang
Published: April 2018

Recent compelling research has demonstrated a pathophysiologic role for proinflammatory cytokines of microglial origin in decreasing neurocognitive function. Psychiatric diseases are already known to have reduced cognitive function and are also associated with increased inflammation. To elaborate on these data, our study aims to investigate how a particular polymorphism of the tumor necrosis factor gene, TNF‐α −1031T/C, affects neurocognitive performance in patients with schizophrenia. We recruited 905 patients with schizophrenia and 571 healthy control subjects. We employed the Repeatable Battery for the Assessment of Neuropsychological Status (RBANS) to test for neurocognitive function and the positive and negative syndrome scale to evaluate schizophrenia severity. The −1031T/C polymorphism was genotyped in both healthy controls and schizophrenic patients. Our results demonstrate that patients with the C allele (either T/C or C/C) possessed increased immediate memory index, visuospatial/constructional index, and RBANS total scores as compared to patients without it (p < .05). In healthy controls, there was no significant difference across genotypes (p > .05). Our findings demonstrate that the TNF‐α −1031T/C polymorphism may not play a role in the susceptibility of schizophrenia itself, but may be involved in the cognitive deficits of schizophrenia. This suggests an important role for cytokine signaling in mediating the severity of cognitive dysfunction in schizophrenia.
Fecal bacterial diversity of wild Sichuan snub‐nosed monkeys (Rhinopithecus roxellana)
Authors: Liu Xuecong , Fan Penglai , Che Rongxiao , Li Huan , Yi Lina , Zhao Na , Garber Paul A. , Li Fang , Jiang Zhigang
Published: April 2018

The gastrointestinal tract of primates harbors a complex microbial community, playing an essential role in the degradation of otherwise indigestible structural carbohydrates. The phylogenetic and functional diversity of the bacterial community in the feces as a surrogate for the gastrointestinal tract of wild Sichuan snub‐nosed monkeys (Rhinopithecus roxellana, N = 6) was characterized based on sequence analysis of 16S rRNA genes. A sex comparison was conducted, with a prior hypothesis that the abundances of the bacterial taxa and/or functional categories associated with energy and nutrient metabolism would be higher in adult females (N = 3) due to the higher reproductive costs compared to adult males (N = 3). Ten phyla were identified in all samples, among which Bacteroidetes and Firmicutes were the predominant. Included in the above two phyla, the members of Prevotellaceae (Prevotella in particular) and Ruminococcaceae were highly abundant, which are common bacteria in the gastrointestinal tract of primates and can degrade various structural carbohydrates such as cellulose, hemicellulose, and pectin. This functionality was in line with the high abundances of the metagenomes associated with carbohydrate metabolism. Consistent with our hypothesis, the abundances of the metagenomes associated with energy metabolism, folding/sorting and degradation, glycan biosynthesis and metabolism, and metabolism of amino acids were higher in adult females relative to adult males. Sex differences were also detected in the bacterial community structure, although no sex differences in the proportions of any bacterial taxa were found likely due to the small sample size. These results suggested that gastrointestinal bacterial communities may aid adult females in increasing energy and nutrition utilization efficiencies compared to adult males. Fecal bacterial communities were found to be more similar between individuals in adult females than in adult males. Our study presented the first examination of the fecal bacterial diversity of a little‐studied, endangered foregut fermenter.
Seasonal variation in diet and nutrition of the northern‐most population of Rhinopithecus roxellana
Authors: Hou Rong , He Shujun , Wu Fan , Chapman Colin A. , Pan Ruliang , Garber Paul A. , Guo Songtao , Li Baoguo
Published: April 2018

There is a great deal of spatial and temporal variation in the availability and nutritional quality of foods eaten by animals, particularly in temperate regions where winter brings lengthy periods of leaf and fruit scarcity. We analyzed the availability, dietary composition, and macronutrients of the foods eaten by the northern‐most golden snub‐nosed monkey (Rhinopithecus roxellana) population in the Qinling Mountains, China to understand food choice in a highly seasonal environment dominated by deciduous trees. During the warm months between April and November, leaves are consumed in proportion to their availability, while during the leaf‐scarce months between December and March, bark and leaf/flower buds comprise most of their diet. When leaves dominated their diet, golden snub‐nosed monkeys preferentially selected leaves with higher ratios of crude protein to acid detergent fiber. While when leaves were less available, bark and leaf/flower buds that were high in nonstructural carbohydrates and energy, and low in acid detergent fiber were selected. Southern populations of golden snub‐nosed monkey can turn to eating lichen, however, the population studied here in this lichen‐absent area have adapted to their cool deciduous habitat by instead consuming buds and bark. Carbohydrate and energy rich foods appear to be the critical resources required for the persistence of this species in temperate habitat. The dietary flexibility of these monkeys, both among seasons and populations, likely contributes to their wide distribution over a range of habitats and environments.
Factor analysis of the questionnaire of olfactory disorders in patients with chronic rhinosinusitis
Authors: Mattos Jose L. , Schlosser Rodney J. , DeConde Adam S. , Hyer Madison , Mace Jess C. , Smith Timothy L. , Soler Zachary M.
Published: April 2018

Background

Olfactory‐specific quality of life (QOL) can be measured using the Questionnaire of Olfactory Disorders–Negative Statements (QOD‐NS), which examines various aspects of olfactory dysfunction. It is unknown if certain factors of the QOD‐NS differentially impact QOL.

Methods

Patients with chronic rhinosinusitis (CRS) completed the QOD‐NS, 22‐item Sino‐Nasal Outcome Test (SNOT‐22), Medical Outcomes Study Short Form 6‐D (SF‐6D) health utility measure, and Patient Health Questionnaire‐2 (PHQ‐2) depression screen. Exploratory factor analysis of the QOD‐NS was performed. Associations between QOD‐NS factors and other QOL metrics were analyzed before and after endoscopic sinus surgery (ESS).

Results

Outcomes were examined on 132 patients. The QOD‐NS contains 4 distinct factors. There was no difference in associations between the different factors and baseline clinical characteristics. ESS had greatest effect size (d) on factors 2 and 4 (d = 0.29 and 0.27, respectively, p < 0.05). Postsurgical changes in the SF‐6D and SNOT‐22 had the strongest correlation with factor 2 scores (r = 0.29 and 0.34, respectively, p < 0.05), and changes in the PHQ‐2 had the strongest correlation to factor 3 (r = 0.24, p < 0.05). Abnormal QOD‐NS scores at baseline were associated with effect size increases of 50% to 100% (p < 0.05).

Conclusion

The QOD‐NS measures 4 distinct factors. Eating‐related questions had the greatest improvement after ESS. Health utility and CRS‐specific QOL improvement most strongly associated with factor 2, while PHQ‐2 changes are most highly associated with factor 3, suggesting a differential impact of the factors of the QOD‐NS on varying aspects of QOL.
Partial resection of the middle turbinate during endoscopic sinus surgery for chronic rhinosinusitis does not lead to an increased risk of empty nose syndrome: a cohort study of a tertiary practice
Authors: Tan Neil C.‐W. , Goggin Rachel , Psaltis Alkis J. , Wormald Peter‐John
Published: April 2018

Background

The treatment of the middle turbinate (MT) during endoscopic sinus surgery (ESS) for chronic rhinosinusitis (CRS) remains a contentious issue with arguments both for and against its resection. The purpose of this study was to examine the clinical impact of partial MT resection (PMTR) during ESS, paying particular attention to the risk of developing empty nose syndrome (ENS) and alteration to olfaction.

Methods

This cohort study was performed on prospectively collected data. A total of 177 patients underwent ESS for CRS; 93 had PMTR and 84 MT preservation (MTP). Preoperative data collection included subjective symptom scores as per the Adelaide Disease Severity Score (ADSS), Lund‐Mackay scores, and nasal polyp status. The Empty Nose Syndrome 6‐Item Questionnaire (ENS6Q) was administered by telephone consultation and analyzed alongside postoperative symptom scores.

Results

There was no difference in ENS6Q scores in patients who underwent PMTR vs those who had MTP. Patients who underwent PMTR had a higher baseline disease on Lund‐Mackay scoring, and were more likely to be nasal polyp patients and be undergoing revision surgery. ADSS scores demonstrated significant improvements in all rhinologic symptoms, with no difference between the cohorts.

Conclusion

PMTR is an adjunctive procedure to ESS. This study has established that PMTR as performed by the senior author carries no additional risk of developing ENS symptoms as defined by the ENS6Q, and that it carries no additional risk to olfaction or other rhinologic symptoms. PMTR can be safely considered at time of ESS, especially in patients at risk of lateralization of the MT.
Italy's ‘Required Initial Mediation Session’: Bridging The Gap between Mandatory and Voluntary Mediation
Authors: D'Urso Leonardo
Published: April 2018

Since the mid‐1990s, an animated debate has been carried out among practitioners, academics and lawmakers about the most effective approach to increase the embrace of mediation in a given jurisdiction, especially outside the United States.
The Humble Neutral, At Your Service
Authors: Creo Robert A.
Published: April 2018

Humility is considered a virtue.
Synthesis and Stereochemical Revision of the C31–C67 Fragment of Amphidinol 3
Authors: Wakamiya Yuma , Ebine Makoto , Murayama Mariko , Omizu Hiroyuki , Matsumori Nobuaki , Murata Michio , Oishi Tohru
Published: April 2018

Amphidinol 3 (AM3) is a marine natural product produced by the dinoflagellate Amphidinium klebsii. Although the absolute configuration of AM3 was determined in 1999 by extensive NMR analysis and degradation of the natural product, it was a daunting task because of the presence of numerous stereogenic centers on the acyclic carbon chain and the limited availability from natural sources. Thereafter, revisions of the absolute configurations at C2 and C51 were reported in 2008 and 2013, respectively. Reported herein is the revised absolute configuration of AM3: 32S, 33R, 34S, 35S, 36S, and 38S based on the chemical synthesis of partial structures corresponding to the C31–C67 fragment of AM3 in combination with degradation of the natural product. The revised structure is unique in that both antipodal tetrahydropyran counterparts exist on a single carbon chain. The structural revision of AM3 may affect proposed structures of congeners related to the amphidinols.
In Vitro Biosynthesis of the Nonproteinogenic Amino Acid Methoxyvinylglycine
Authors: Patteson Jon B. , Dunn Zachary D. , Li Bo
Published: April 2018

Oxyvinylglycines are a family of nonproteinogenic amino acids featuring an essential vinyl ether conferring mechanism‐based inhibition of pyridoxal phosphate enzymes. The gene clusters for a few oxyvinylglycines are known, yet the biosynthetic origin of the vinyl ether is elusive. The in vitro biosynthesis of methoxyvinylglycine or l‐2‐amino‐4‐methoxy‐trans‐3‐butenoic acid (AMB) is reported. It is shown that AMB is made from glutamate as an alanyl‐AMB dipeptide and the rationale is provided for the N‐term Ala. Using a chemical capture method, the order and timing of the modifications on non‐ribosomal peptide synthetase (NRPS)‐bound substrates was determined, including a cryptic hydroxylation of the Glu β‐carbon. Eliminating this hydroxy group likely generates a key α,β‐dehydroamino acid intermediate that facilitates decarboxylation. This work sheds light on vinyl ether biosynthesis and uncovers new NRPS chemistry.
Versatile Three‐Dimensional Porous Cu@Cu2O Aerogel Networks as Electrocatalysts and Mimicking Peroxidases
Authors: Ling Pinghua , Zhang Qiang , Cao Tingting , Gao Feng
Published: April 2018

A facile strategy is presented to form 3D porous Cu@Cu2O aerogel networks by self‐assembling Cu@Cu2O nanoparticles with the diameters of ca. 40 nm for constructing catalytic interfaces. Unexpectedly, the prepared Cu@Cu2O aerogel networks display excellent electrocatalytic activity to glucose oxidation at a low onset potential of ca. 0.25 V. Moreover, the Cu@Cu2O aerogels also can act as mimicking‐enzymes including horseradish peroxidase and NADH peroxidase, and show obvious enzymatic catalytic activities to the oxidation of dopamine (DA), o‐phenyldiamine (OPD), 3,3,5,5‐tetramethylbenzidine (TMB), and dihydronicotinamide adenine dinucleotide (NADH) in the presence of H2O2. These 3D Cu@Cu2O aerogel networks are a new class of porous catalytic materials as mimic peroxidases and electrocatalysts and offer a novel platform to construct catalytic interfaces for promising applications in electrochemical sensors and artificial enzymatic catalytic systems.
Mapping the Excited‐State Potential Energy Surface of a Photomolecular Motor
Authors: Hall Christopher R. , Browne Wesley R. , Feringa Ben L. , Meech Stephen R.
Published: April 2018

A detailed understanding of the operation and efficiency of unidirectional photomolecular rotary motors is essential for their effective exploitation in molecular nanomachines. Unidirectional motion relies on light‐driven conversion from a stable (1 a) to a metastable (1 b) conformation, which then relaxes through a thermally driven helix inversion in the ground state. The excited‐state surface has thus far only been experimentally characterised for 1 a. Here we probe the metastable, 1 b, excited state, utilising ultrafast transient absorption and femtosecond stimulated Raman spectroscopy. These reveal that the “dark” excited‐state intermediate between 1 a and 1 b has a different lifetime and structure depending on the initial ground‐state conformation excited. This suggests that the reaction coordinate connecting 1 a to 1 b differs to that for the reverse photochemical process. The result is contrasted with earlier calculations.
Chemiluminescent Probes for Activity‐Based Sensing of Formaldehyde Released from Folate Degradation in Living Mice
Authors: Bruemmer Kevin J. , Green Ori , Su Timothy A. , Shabat Doron , Chang Christopher J.
Published: April 2018

Formaldehyde (FA) is a common environmental toxin that is also produced naturally in the body through a wide range of metabolic and epigenetic processes, motivating the development of new technologies to monitor this reactive carbonyl species (RCS) in living systems. Herein, we report a pair of first‐generation chemiluminescent probes for selective formaldehyde detection. Caging phenoxy‐dioxetane scaffolds bearing different electron‐withdrawing groups with a general 2‐aza‐Cope reactive formaldehyde trigger provides chemiluminescent formaldehyde probes 540 and 700 (CFAP540 and CFAP700) for visible and near‐IR detection of FA in living cells and mice, respectively. In particular, CFAP700 is capable of visualizing FA release derived from endogenous folate metabolism, providing a starting point for the use of CFAPs and related chemical tools to probe FA physiology and pathology, as well as for the development of a broader palette of chemiluminescent activity‐based sensing (ABS) probes that can be employed from in vitro biochemical to cell to animal models.
Dynamic Nuclear Polarization NMR Spectroscopy of Polymeric Carbon Nitride Photocatalysts: Insights into Structural Defects and Reactivity
Authors: Li Xiaobo , Sergeyev Ivan V. , Aussenac Fabien , Masters Anthony F. , Maschmeyer Thomas , Hook James M.
Published: April 2018

Metal‐free polymeric carbon nitrides (PCNs) are promising photocatalysts for solar hydrogen production, but their structure–photoactivity relationship remains elusive. Two PCNs were characterized by dynamic‐nuclear‐polarization‐enhanced solid‐state NMR spectroscopy, which circumvented the need for specific labeling with either 13C‐ or 15N‐enriched precursors. Rapid 1D and 2D data acquisition was possible, providing insights into the structural contrasts between the PCNs. Compared to PCN_B with lower performance, PCN_P is a more porous and more active photocatalyst that is richer in terminal N−H bonds not associated with interpolymer chains. It is proposed that terminal N−H groups act as efficient carrier traps and reaction sites.
Goldkatalysierte, regiospezifische C‐H‐Anellierung von ortho‐Ethinylbiarylen mit Anthranilen: π‐Extension durch Ringerweiterung auf dem Weg zu N‐haltigen PAKs
Authors: Zeng Zhongyi , Jin Hongming , Sekine Kohei , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K.
Published: April 2018

Wir beschreiben einen neuen, kurzen und flexiblen Weg zu verschiedenen N‐haltigen polycyclischen aromatischen Kohlenwasserstoffen (PAK) über eine goldkatalysierte π‐Erweiterungsreaktion von Anthranilen mit o‐Ethinylbiarylen als Reagenzien. Diese Strategie nutzt leicht zugängliche Edukte, ist aufgrund einer hohen Stufen‐ und Atomökonomie einfach und zeigt eine gute Toleranz gegenüber funktionellen Gruppen, ein Hochskalieren ist ebenfalls möglich. Der mechanistische Vorschlag für die Tandemreaktion beinhaltet eine nukleophile Addition/Ringöffnung/regiospezifische C‐H‐Anellierung/Protodesaurierung und abschließend eine Friedel‐Crafts‐artige Cyclisierung. Photophysikalische Studien der Produkte zeigen eine violett‐blaue Fluoreszenz mit einer Quantenausbeute von bis zu 0.45.
Catalytic Dinitrogen Reduction to Ammonia at a Triamidoamine–Titanium Complex
Authors: Doyle Laurence R. , Wooles Ashley J. , Jenkins Lucy C. , Tuna Floriana , McInnes Eric J. L. , Liddle Stephen T.
Published: April 2018

Catalytic reduction of N2 to NH3 by a Ti complex has been achieved, thus now adding an early d‐block metal to the small group of mid‐ and late‐d‐block metals (Mo, Fe, Ru, Os, Co) that catalytically produce NH3 by N2 reduction and protonolysis under homogeneous, abiological conditions. Reduction of [TiIV(TrenTMS)X] (X=Cl, 1A; I, 1B; TrenTMS=N(CH2CH2NSiMe3)3) with KC8 affords [TiIII(TrenTMS)] (2). Addition of N2 affords [{(TrenTMS)TiIII}2(μ‐η1:η1‐N2)] (3); further reduction with KC8 gives [{(TrenTMS)TiIV}2(μ‐η1:η1:η2:η2‐N2K2)] (4). Addition of benzo‐15‐crown‐5 ether (B15C5) to 4 affords [{(TrenTMS)TiIV}2(μ‐η1:η1‐N2)][K(B15C5)2]2 (5). Complexes 3–5 treated under N2 with KC8 and [R3PH][I], (the weakest H+ source yet used in N2 reduction) produce up to 18 equiv of NH3 with only trace N2H4. When only acid is present, N2H4 is the dominant product, suggesting successive protonation produces [{(TrenTMS)TiIV}2(μ‐η1:η1‐N2H4)][I]2, and that extruded N2H4 reacts further with [R3PH][I]/KC8 to form NH3.
Cleavable Binary Dyads: Simplifying Data Extraction and Increasing Storage Density in Digital Polymers
Authors: Cavallo Gianni , Poyer Salomé , Amalian Jean‐Arthur , Dufour Florent , Burel Alexandre , Carapito Christine , Charles Laurence , Lutz Jean‐François
Published: April 2018

Digital polymers are uniform macromolecules that store monomer‐based binary sequences. Molecularly stored information is usually extracted from the polymer by a tandem mass spectrometry (MS/MS) measurement, in which the coded chains are fragmented to reveal each bit (i.e. basic coded monomer unit) of the sequence. Here, we show that data‐extraction can be greatly simplified by favoring the formation of MS/MS fragments containing two bits instead of one. In order to do so, digital poly(alkoxyamine phosphodiester)s, containing binary dyads in each repeat unit, were prepared by an orthogonal solid‐phase approach involving successive phosphoramidite and radical‐radical coupling steps. Three different sets of monomers were considered to build these polymers. In all cases, four coded building blocks—two hydroxy‐nitroxides and two phosphoramidite monomers—were required to build the dyads. Among the three studied monomer sets, one combination allowed synthesis of uniform sequence‐coded polymers. The resulting polymers led to clear dyad‐containing fragments in MS/MS and could therefore be efficiently decoded. Additionally, an algorithm was created to detect specific dyad fragments, thus enabling automated sequencing.
In Situ Monitoring of RAFT Polymerization by Tetraphenylethylene‐Containing Agents with Aggregation‐Induced Emission Characteristics
Authors: Liu Shunjie , Cheng Yanhua , Zhang Haoke , Qiu Zijie , Kwok Ryan T. K. , Lam Jacky W. Y. , Tang Ben Zhong
Published: April 2018

A facile and efficient approach is demonstrated to visualize the polymerization in situ. A group of tetraphenylethylene (TPE)‐containing dithiocarbamates were synthesized and screened as agents for reversible addition fragmentation chain transfer (RAFT) polymerizations. The spatial‐temporal control characteristics of photochemistry enabled the RAFT polymerizations to be ON and OFF on demand under alternating visible light irradiation. The emission of TPE is sensitive to the local viscosity change owing to its aggregation‐induced emission characteristic. Quantitative information could be easily acquired by the naked eye without destroying the reaction system. Furthermore, the versatility of such a technique was well demonstrated by 12 different polymerization systems. The present approach thus demonstrated a powerful platform for understanding the controlled living radical polymerization process.
Gold‐Catalyzed Regiospecific C−H Annulation of o‐Ethynylbiaryls with Anthranils: π‐Extension by Ring‐Expansion En Route to N‐Doped PAHs
Authors: Zeng Zhongyi , Jin Hongming , Sekine Kohei , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K.
Published: April 2018

We describe a novel, short, and flexible approach to diverse N‐doped polycyclic aromatic hydrocarbons (PAHs) through gold‐catalyzed π‐extension of anthranils with o‐ethynylbiaryls as reagents. This strategy uses easily accessible starting materials, is simple due to high step and atom economy, and shows good functional‐group compatibility as well as scale‐up potential. Mechanistically, the tandem reaction is proposed to involve a nucleophilic addition/ring opening/regiospecific C−H annulation/protodeauration sequence terminated by a Friedel–Crafts‐type cyclization. Photophysical studies of the products indicated violet‐blue fluorescence emission with quantum yields up to 0.45.
Propagation of Enzyme‐Induced Surface Events inside Polymer Nanoassemblies for a Fast and Tunable Response
Authors: Zhuang Jiaming , Seçinti Hatice , Zhao Bo , Thayumanavan S.
Published: April 2018

We report a new molecular design strategy that allows for the propagation of surface enzymatic events inside a supramolecular assembly for accelerated molecular release. The approach addresses a key shortcoming encountered with many of the currently available enzyme‐induced disassembly strategies, which rely on the unimer–aggregate equilibria of amphiphilic assemblies. The enzymatic response of the host to predictably tune the kinetics of guest‐molecule release can be programmed by controlling substrate accessibility through electrostatic complexation with a complementary polymer. Accelerated guest release in response to the enzyme is shown to be accomplished by a cooperative mechanism of enzyme‐triggered supramolecular host disassembly and host reorganization.
Political assumptions underlying pedagogies of national education: The case of student teachers teaching ‘British values’ in England
Authors: Sant Edda , Hanley Chris
Published: April 2018

Teacher education in England now requires that student teachers follow practices that do not undermine “fundamental British values” where these practices are assessed against a set of ethics and behaviour standards. This paper examines the political assumptions underlying pedagogical interpretations about the education of national identities through documenting how a group of student teachers uphold the institutional demand of promoting fundamental British Values in relation to their discursive constructions of Britishness. Empirical data exemplifies potential political understandings guiding educational practices. Analysis suggests that pedagogies of national education are mediated by (i) educators’ understandings of the nation as an essential entity or a social construct and (ii) their understanding of national identities as being open or closed to competing interpretations. The paper concludes by examining implications of different political and pedagogical positions for practice and research.
miRNAs – der Hacker‐Angriff der Parasiten
Authors: Köster Tino
Published: April 2018

Die parasitische Pflanze Cuscuta campestris legt in der Wirtspflanze mit Hilfe von microRNAs die Expression von Genen lahm, die der Verteidigung gegen den Parasiten dienen. So kann der Parasit sich an den Nährstoffen der Wirtspflanze bedienen.
Seeschlangen streifen Schadstoffe mit der schwarzen Haut ab
Authors: Kronberg Inge
Published: April 2018

Anders als viele andere Polymorphismen ist die Melanisierung eine optisch leicht nachweisbare Veränderung, die sich noch dazu sehr schnell in Populationen verbreitet. Für evolutionsbiologische Untersuchungen ist sie daher bestens geeignet. Melanisierungen kennt man nicht nur von Insekten, sondern auch von Wirbeltieren. Sie können aus unterschiedlichen Gründen vorteilhaft sein. Bei Seeschlangen steigert eine Melanisierung die Ausscheidung von Spurenmetallen.
Bockkäfer auf Blüten
Authors: Petrischak Hannes
Published: April 2018

Nicht nur Bienen und Schmetterlinge sind eifrige Blütenbesucher – zahlreiche Käfer schätzen ebenfalls Pollen und Nektar als Nahrung. Unter ihnen stechen die Bockkäfer (Cerambycidae) hervor, die mit ihren langen, gebogenen Fühlern und teilweise lebhaften Farben zu den besonders attraktiven Insekten zählen. Phänomene wie Wespen‐Mimikry und die häufige Bindung an Totholz machen sie auch aus ökologischer Sicht interessant.
Nachrichten des Verbandes Biologie, Biowissenschaften & Biomedizin in Deutschland
Authors: Lohmeier Uwe
Published: April 2018

Aus den Fachgesellschaften

Wissenschaft & Gesellschaft

Koalitionsvertrag

Access and Benefit Sharing

March for Science 2018

In eigener Sache
Humanistic‐experiential therapies in the treatment of generalised anxiety: A perspective
Authors: Timulak Ladislav
Published: April 2018

This study discusses the current status of evidence‐based psychological therapies for generalised anxiety disorder (GAD). It points to the dominance of cognitive‐behavioural therapies (CBTs) and compares this dominance with the position of humanistic‐experiential therapies (HEPs) in this area. The paper hypothesises several reasons for this situation, including historical developments as well as HEPs’ ambivalence around embracing mainstream mental health classification systems, and corresponding types of research. The paper then highlights some recent developments in HEPs for anxiety disorders (particularly emotion‐focused therapy; EFT); developments that are breaking new conceptual grounds while also generating new outcome research.
Popolohuanones G – I, Dimeric Sesquiterpene Quinones with IL‐6 Inhibitory Activity from the Marine Sponge Dactylospongia elegans
Authors: Li Jing , Wu Wei , Yang Fan , Liu Li , Wang Shu‐Ping , Jiao Wei‐Hua , Xu Shi‐Hai , Lin Hou‐Wen
Published: April 2018

Chemical investigation of the marine sponge Dactylospongia elegans, collected from the South China Sea, afforded three new dimeric sesquiterpene quinones, popolohuanones G – I (1 – 3), together with two known analogs, popolohuanones B (4) and C (5). The new structures were determined by HR‐ESI‐MS and 1D‐ and 2D‐NMR analyses. All the five compounds showed no cytotoxic activity against five human cancer cell lines, while popolohuanone H (2) showed potent inhibitory activity against IL‐6, an inflammatory cytokine, at the concentration of 10 μm.
Looking for the bare necessities
Authors: Krishnan Sandeep K. , Dean Larry S.
Published: April 2018

Key Points

The authors suggest that the early durability of the CoreValve implant should not be in question based on the results of this modestly sized, but well‐done postmortem observational study.

Given the ever‐expanding knowledge of valvular degeneration, one thing is clear: more research and study is needed before any routine change in clinical practice, such as change it antithrombotic therapy, can be recommended.

Further autopsy studies of patients who die outside of typical healthcare settings and who have had a longer median implant time would aid greatly in furthering the understanding of the degeneration and natural history of bioprosthetic transcatheter heart valves.
Early stent thrombosis: Nearly gone, but never forgotten
Authors: Seto Arnold H. , Kern Morton J.
Published: April 2018

Key Points

Early stent thrombosis occurs in ∼1% of patients treated with primary PCI and increases shock, stroke, and mortality.

Early stent thrombosis was associated with small stent diameter, failure to use glycoprotein inhibitors, and bivalirudin use.

Minimizing stent thrombosis may require the use of imaging and aggressive antithrombotic therapy
The quest for a “diabetic” stent
Authors: Khan Asaad A. , Dangas George D.
Published: April 2018

Key Points

Patients with diabetes mellitus and extensive coronary artery disease generally had worse outcomes with early generation drug eluting stents (DES) as compared to coronary artery bypass grafting.

Initial results with Amphilimus eluting coronary stent in patients with diabetes have been promising in small studies

The data from Sardella et al. should be used, in conjunction with previous clinical studies with this DES type, as hypothesis generating for a large multicenter randomized trial to aid in our quest to find the “new diabetic stent.”
TAVR technique tries to go higher than bicuspid valve hurdles
Authors: Burzotta Francesco , Trani Carlo
Published: April 2018

Key Points

Aortic stenosis developed in bicuspid valves is commonly characterized by a complex anatomy

TAVR may be considered for high risk patients with bicuspid valve stenosis but procedure is usually technically challenging

High (supra‐annular) implantation of self‐expandable TAVR prostheses may be a valuable option for selected patients with bicuspid valve stenosis
Heteroatomic Zn‐MWW Zeolite Developed for Catalytic Dehydrogenation Reactions: A Combined Experimental and DFT Study
Authors: Yan Wenjin , Xi Shibo , Du Yonghua , Schreyer Martin K. , Tan Sze Xing , Liu Yan , Borgna Armando
Published: April 2018

To incorporate divalent transition metals into molecular sieve frameworks remains a great challenge in zeolite chemistry. In this study, Zn was successfully incorporated inside the MWW zeolite framework, namely Zn‐MWW (Zn−Si), through hydrothermal synthesis. A combined DFT and X‐ray absorption near edge structure (XANES) simulation was applied to unravel the location of Zn inside the structure, indicating that the most plausible Zn position is T5 with two sodium cations close to the neighboring oxygen to neutralize the charge of the zeolite. The as‐synthesized material exhibits superior catalytic performance for 1‐butene oxidative dehydrogenation with CO2 compared with MCM‐22 and ITQ‐1 supported ZnO. The 1,3‐butadiene (BD) selectivity is doubled at similar 1‐butene conversions. On the other hand, more than 51 % acetaldehyde is produced during ethanol conversion on the Zn‐MWW zeolite, whereas MCM‐22 mainly gives ethylene. The remarkable performance is associated with the efficient combination of acidity and redox properties owing to the successful insertion of atomic Zn inside the MWW framework, as demonstrated by XRD, FTIR, 29Si MAS NMR, XANES analysis, and DFT simulations.
Gulf‐Selective Postsynthetic Functionalization of a Soluble Hexabenzoovalene
Authors: Baumgärtner Kevin , Rominger Frank , Mastalerz Michael
Published: April 2018

The interest in 2D‐annulated polycyclic aromatic hydrocarbons (PAHs) has risen in recent years due to promising applications in using PAHs for organic electronics. The larger the PAHs, the more insoluble they are, making their characterization and especially selective functionalization difficult. Triptycene end‐capping has been introduced to circumvent the problem of low solubility of a hexabenzoovalene (HBO). Additionally, the tendency to form single‐crystals for X‐ray diffraction is preserved. The good solubility of the HBO makes it possible to selectively difunctionalize the compound in the “gulf” region to change electronic properties of the π‐system, which has been investigated photophysically as well as electrochemically.
3D Hierarchical Microballs Constructed by Intertwined MnO@N‐doped Carbon Nanofibers towards Superior Lithium‐Storage Properties
Authors: Li Yi‐Jing , Fan Chao‐Ying , Li Huan‐Huan , Huang Ke‐Cheng , Zhang Jing‐Ping , Wu Xing‐Long
Published: April 2018

MnO is a promising high‐capacity anode material for lithium‐ion batteries (LIBs), but pristine material suffers short cycle life and poor rate capability, thus hindering the practical application. In this work, a new type of porous MnO microballs stringed with N‐doped porous carbon (3DHB‐MnO@NC) with a well‐connected hierarchical three‐dimensional network structure was prepared by the facile self‐template method. The 3DHB‐MnO@NC electrode can effectively promote the ion/electron transfer and buffer the large volume change of electrode during the electrochemical reaction. As the anode for LIBs, the 3DHB‐MnO@NC possesses outstanding cycling performance (1247.7 mA h g−1 after 90 cycles at 200 mA g−1) and good rate capabilities (949.6 mA h g−1 after 450 cycles at 1000 mA g−1). The facile self‐template method of the prepared 3DHB‐MnO@NC composite paves a new way for practical applications of MnO in high performance LIBs.