bluuebunny/crossref_metadata_2025_split huggingface dataset:
Single‐Point Remote Control of Flapping Motion in Clothespin‐Shaped Bimetallic Palladium Complexes Based on the N(sp2)–N(sp3) Interconversion in Amide Functionalities
Authors: Inoue Ryo , Kawamorita Soichiro , Naota Takeshi 
Published: March 2016

AbstractThe synthesis, structure, and flapping motion of clothespin‐shaped binuclear trans‐bis(salicylaldiminato)palladium(II) complexes (anti‐1) with 4‐azaheptamethylene linkers bearing amide (a–g), urethane (h), or urea (i) functionalities are described in this report. Various 2D 1H NMR experiments and XRD analyses indicate that the amide‐ and urethane‐linked anti‐1 a,b,d–h complexes exist as equilibrated mixtures of major and minor conformers I and II in CDCl3, whereas the complexes anti‐1 c and i were observed as a single species. The mapping of NOESY cross‐peaks between conformers I and II revealed that the equilibration of the major and minor conformers of anti‐1 a,b,d–h proceeds by two pathways, namely a nonrotatory flapping motion of the coordinated blades and a nonflapping rotation of C−N bonds, whereas the equilibration of anti‐1 c proceeds by simultaneous flapping and rotation motions. Kinetic studies carried out by means of 1H–1H EXSY experiments revealed that 1) the ΔG≠298K values for the flapping motion are controlled remotely by the steric and electronic effects of the RCON functionalities and 2) the activation parameters for the nonrotatory flapping process are identical to those for the nonflapping peptide rotation in the complexes anti‐1 a,b,d–h, which indicates that the present multistep conformational transformation induced by the flapping motion is controlled by the rate‐determining pyramidalization/depyramidalization (i.e., sp2/sp3 interconversion) of the nitrogen atoms of the functionalities. The static and controllable molecular mobility of anti‐1 bearing peptide linkers has been discussed by comparison with the dynamic behavior of its analogues anti‐2–4 with flexible polymethylene linkers.
Structure‐Dependent Anchoring of Organic Molecules to Atomically Defined Oxide Surfaces: Phthalic Acid on Co3O4(111), CoO(100), and CoO(111)
Authors: Xu Tao , Schwarz Matthias , Werner Kristin , Mohr Susanne , Amende Max , Libuda Jörg 
Published: March 2016

AbstractWe have performed a model study to explore the influence of surface structure on the anchoring of organic molecules on oxide materials. Specifically, we have investigated the adsorption of phthalic acid (PA) on three different, well‐ordered, and atomically defined cobalt oxide surfaces, namely 1) Co3O4(111), 2) CoO(111), and 3) CoO(100) on Ir(100). PA was deposited by physical vapor deposition (PVD). The formation of the PA films and interfacial reactions were monitored in situ during growth by isothermal time‐resolved IR reflection absorption spectroscopy (TR‐IRAS) under ultrahigh vacuum (UHV) conditions. We observed a pronounced structure dependence on the three surfaces with three distinctively different binding geometries and characteristic differences depending on the temperature and coverage. 1) PA initially binds to Co3O4(111) through the formation of a chelating bis‐carboxylate with the molecular plane oriented perpendicularly to the surface. Similar species were observed both at low temperature (130 K) and at room temperature (300 K). With increasing exposure, chelating mono‐carboxylates became more abundant and partially replaced the bis‐carboxylate. 2) PA binds to CoO(100) in the form of a bridging bis‐carboxylate for low coverage. Upon prolonged deposition of PA at low temperature, the bis‐carboxylates were converted into mono‐carboxylate species. In contrast, the bis‐carboxylate layer was very stable at 300 K. 3) For CoO(111) we observed a temperature‐dependent change in the adsorption mechanism. Although PA binds as a mono‐carboxylate in a bridging bidentate fashion at low temperature (130 K), a strongly distorted bis‐carboxylate was formed at 300 K, possibly as a result of temperature‐dependent restructuring of the surface. The results show that the adsorption geometry of PA depends on the atomic structure of the oxide surface. The structure dependence can be rationalized by the different arrangements of cobalt ions at the three surfaces.
Magnetic N‐Enriched Fe3C/Graphitic Carbon instead of Pt as an Electrocatalyst for the Oxygen Reduction Reaction
Authors: Wang Xiaobai , Zhang Peng , Wang Wei , Lei Xiang , Yang Hua 
Published: March 2016

AbstractA series of Fe3C/C‐Nx nanoparticles (NPs) with different nitrogen content are prepared by a simple one‐pot route. In the synthetic procedure, aniline and acetonitrile are simultaneously used as the carbon and nitrogen source. The effect of calcination temperature on the structural and functional properties of the materials is investigated. Magnetic measurement shows that the sample prepared at 800 °C (Fe3C/C‐N800 NPs) possesses the highest Ms value of 77.2 emu g−1. On testing as oxygen reduction reaction (ORR) catalysts, the sample prepared at 750 °C (Fe3C/C‐N750 NPs) shows the best ORR performance among the series, with a more positive onset potential (+0.99 V vs. RHE), higher selectivity (number of electron transfer n≈3.93), longer durability, and stronger tolerance against methanol crossover than commercial Pt/C catalysts in a 0.1 m KOH solution. Moreover, in acidic solution, the excellent ORR activity and stability are also exhibited.
Catalase‐Modified Carbon Electrodes: Persuading Oxygen To Accept Four Electrons Rather Than Two
Authors: Sepunaru Lior , Laborda Eduardo , Compton Richard G. 
Published: March 2016

AbstractWe successfully exploited the natural highly efficient activity of an enzyme (catalase) together with carbon electrodes to produce a hybrid electrode for oxygen reduction, very appropriate for energy transformation. Carbon electrodes, in principle, are cheap but poor oxygen reduction materials, because only two‐electron reduction of oxygen occurs at low potentials, whereas four‐electron reduction is key for energy‐transformation technology. With the immobilization of catalase on the surface, the hydrogen peroxide produced electrochemically is decomposed back to oxygen by the enzyme; the enzyme natural activity on the surface regenerates oxygen, which is further reduced by the carbon electrode with no direct electron transfer between the enzyme and the electrode. Near full four‐electron reduction of oxygen is realised on a carbon electrode, which is modified with ease by a commercially available enzyme. The value of such enzyme‐modified electrode for energy‐transformation devices is evident.
Problematik der Übertragbarkeit bestehender Verfahren zur Kunststoff‐Charakterisierung auf Kunststoffgemische
Authors: Forberger Jens , Becker Robert W. 
Published: March 2016

AbstractDie Rückgewinnung von Stoffmengen aus Verbundwerkstoffen im Sinne von Molecular Sorting ist ökonomisch attraktiv, wenn möglichst viele Stoffgruppen identifiziert, separiert und in den Stoffkreislauf zurückgeführt werden können. Durch Recycling von Thermoplast‐Matrix oder neue Entwicklungen zur werkstofflichen Verwertung von Verbundwerkstoffen werden neue Stoffstrome zurück in den Primärmarkt generiert. Jedoch bereits bei der Materialanalyse sind bestehende Verfahren beispielsweise für die Unternehmen wenig praxistauglich und stehen daher nur eingeschränkt zur Verfügung. Auch hochwertige Lösungen zur Erfassung, Charakterisierung und Verarbeitung von Verbundsystemen verschiedenster Kunststofftypen können nur eingeschränkt eingesetzt werden.
N‐Benzyl‐4‐((heteroaryl)methyl)benzamides: A New Class of Direct NADH‐Dependent 2‐trans Enoyl–Acyl Carrier Protein Reductase (InhA) Inhibitors with Antitubercular Activity
Authors: Guardia Ana , Gulten Gulcin , Fernandez Raquel , Gómez Jesus , Wang Feng , Convery Maire , Blanco Delia , Martínez María , Pérez‐Herrán Esther , Alonso Marta , Ortega Fátima , Rullás Joaquín , Calvo David , Mata Lydia , Young Robert , Sacchettini James C. , Mendoza‐Losana Alfonso , Remuiñán Modesto , Ballell Pages Lluís , Castro‐Pichel Julia 
Published: March 2016

AbstractIsoniazid (INH) remains one of the cornerstones of antitubercular chemotherapy for drug‐sensitive strains of M. tuberculosis bacteria. However, the increasing prevalence of multidrug‐resistant (MDR) and extensively drug‐resistant (XDR) strains containing mutations in the KatG enzyme, which is responsible for the activation of INH into its antitubercular form, have rendered this drug of little or no use in many cases of drug‐resistant tuberculosis. Presented herein is a novel family of antitubercular direct NADH‐dependent 2‐trans enoyl–acyl carrier protein reductase (InhA) inhibitors based on an N‐benzyl‐4‐((heteroaryl)methyl)benzamide template; unlike INH, these do not require prior activation by KatG. Given their direct InhA target engagement, these compounds should be able to circumvent KatG‐related resistance in the clinic. The lead molecules were shown to be potent inhibitors of InhA and showed activity against M. tuberculosis bacteria. This new family of inhibitors was found to be chemically tractable, as exemplified by the facile synthesis of analogues and the establishment of structure–activity relationships. Furthermore, a co‐crystal structure of the initial hit with the enzyme is disclosed, providing valuable information toward the design of new InhA inhibitors for the treatment of MDR/XDR tuberculosis.
Quantitative Detection of Nucleoside Analogues by Multi‐enzyme Biosensors using Time‐Resolved Kinetic Measurements
Authors: Muthu Pravin , Lutz Stefan 
Published: March 2016

AbstractFast, simple and cost‐effective methods for detecting and quantifying pharmaceutical agents in patients are highly sought after to replace equipment and labor‐intensive analytical procedures. The development of new diagnostic technology including portable detection devices also enables point‐of‐care by non‐specialists in resource‐limited environments. We have focused on the detection and dose monitoring of nucleoside analogues used in viral and cancer therapies. Using deoxyribonucleoside kinases (dNKs) as biosensors, our chemometric model compares observed time‐resolved kinetics of unknown analytes to known substrate interactions across multiple enzymes. The resulting dataset can simultaneously identify and quantify multiple nucleosides and nucleoside analogues in complex sample mixtures.
Current international flow cytometric practices for the detection and monitoring of paroxysmal nocturnal haemoglobinuria clones: A UK NEQAS survey
Authors: Fletcher Matthew , Whitby Liam , Whitby Alison , Barnett David 
Published: March 2016

BackgroundParoxysmal nocturnal haemoglobinuria (PNH) is a rare acquired genetic disorder, with an incidence of approximately 1.3 new cases per million population per year. Evidence from the UK National External Quality Assessment Service for Leucocyte Immunophenotyping (UK NEQAS LI) programme suggested major discrepancies on how PNH testing is undertaken. To investigate this we surveyed laboratories in the UK NEQAS LI PNH programme and report here the findings.MethodsA questionnaire was distributed to all centres registered in UK NEQAS LI flow cytometry programmes (n = 1587). Comprising several subsections, it covered the majority of clinical flow cytometric practices. Participants completed a general section and then the subsections relevant to their laboratory repertoire. One subsection contained 34 questions regarding practices in PNH clone detection.ResultsA total of 105 laboratories returned results for the PNH section; the results demonstrated lack of consensus in all areas of PNH testing. Variation was seen in gating and testing strategies, sensitivity levels and final reporting of test results. Several incorrect practices were highlighted such as inappropriate antibody selection and failure to wash the red blood cells (RBCs) prior to analysis.ConclusionDespite the availability of consensus guidelines there appears to be no agreement in the detection and monitoring of PNH. We found only fourteen centres using methods compatible with the International Clinical Cytometry Society guidelines. Of specific note we found that no two laboratories used the same method. This technical variation could lead to incorrect diagnoses, highlighting the need for better adoption and understanding of consensus practices. © 2016 International Clinical Cytometry Society
Acute heat shock leads to cortical domain internalization and polarity loss in the C. elegans embryo
Authors: Singh Deepika , Odedra Devang , Lehmann Christina , Pohl Christian 
Published: March 2016

SummaryMany developmental processes are inherently robust due to network organization of the participating factors and functional redundancy. The heterogeneity of the factors involved and their connectivity puts these processes at risk of abrupt system collapse under stress. The polarization of the one‐cell C. elegans embryo constitutes such an inherently robust process with functional redundancy. However, how polarization is affected by acute stress has not been thoroughly investigated. Here, we report that heat shock (34°C, 1 h) triggers a highly reproducible loss of the anterior and collapse of the posterior polarity domains. Temperature‐dependent loss of cortical non‐muscle myosin II drastically reduces cortical tension and leads to internalization of large plasma membrane domains including the membrane‐associated polarity factor PAR‐2. After internalization, plasma membrane vesicles and associated factors cluster around centrosomes and are thereby withdrawn from the polarization process. Transient formation of the posterior polarity domain suggests that microtubule‐induced self‐organization of this domain is not compromised after heat shock. Hence, our data uncover that the polarization system undergoes a temperature‐dependent collapse under acute stress. genesis, 2016. © 2016 Wiley Periodicals, Inc. genesis 54:220–228, 2016. © 2016 Wiley Periodicals, Inc.
The Caenorhabditis elegans Q neuroblasts: A powerful system to study cell migration at single‐cell resolution in vivo
Authors: Rella Lorenzo , Fernandes Póvoa Euclides E. , Korswagen Hendrik C. 
Published: March 2016

SummaryDuring development, cell migration plays a central role in the formation of tissues and organs. Understanding the molecular mechanisms that drive and control these migrations is a key challenge in developmental biology that will provide important insights into disease processes, including cancer cell metastasis. In this article, we discuss the Caenorhabditis elegans Q neuroblasts and their descendants as a tool to study cell migration at single‐cell resolution in vivo. The highly stereotypical migration of these cells provides a powerful system to study the dynamic cytoskeletal processes that drive migration as well as the evolutionarily conserved signaling pathways (including different Wnt signaling cascades) that guide the cells along their specific trajectories. Here, we provide an overview of what is currently known about Q neuroblast migration and highlight the live‐cell imaging, genome editing, and quantitative gene expression techniques that have been developed to study this process. genesis, 2016. © 2016 Wiley Periodicals, Inc. genesis 54:198–211, 2016. © 2016 Wiley Periodicals, Inc.
Automated proximity sensing in small vertebrates: design of miniaturized sensor nodes and first field tests in bats
Authors: Ripperger Simon , Josic Darija , Hierold Martin , Koelpin Alexander , Weigel Robert , Hartmann Markus , Page Rachel , Mayer Frieder 
Published: March 2016

AbstractSocial evolution has led to a stunning diversity of complex social behavior, in particular in vertebrate taxa. Thorough documentation of social interactions is crucial to study the causes and consequences of sociality in gregarious animals. Wireless digital transceivers represent a promising tool to revolutionize data collection for the study of social interactions in terms of the degree of automation, data quantity, and quality. Unfortunately, devices for automated proximity sensing via direct communication among animal‐borne sensors are usually heavy and do not allow for the investigation of small animal species, which represent the majority of avian and mammalian taxa. We present a lightweight animal‐borne sensor node that is built from commercially available components and uses a sophisticated scheme for energy‐efficient communication, with high sampling rates at relatively low power consumption. We demonstrate the basic functionality of the sensor node under laboratory conditions and its applicability for the study of social interactions among free‐ranging animals. The first field tests were performed on two species of bats in temperate and tropical ecosystems. At <2 g, this sensor node is light enough to observe a broad spectrum of taxa including small vertebrates. Given our specifications, the system was especially sensitive to changes in distance within the short range (up to a distance of 4 m between tags). High spatial resolution at short distances enables the evaluation of interactions among individuals at a fine scale and the investigation of close contacts. This technology opens new avenues of research, allowing detailed investigation of events associated with social contact, such as mating behavior, pathogen transmission, social learning, and resource sharing. Social behavior that is not easily observed becomes observable, for example, in animals living in burrows or in nocturnal animals. A switch from traditional methods to the application of digital transceiver chips in proximity sensing offers numerous advantages in addition to an enormous increase in data quality and quantity. For future applications, the platform allows for the integration of additional sensors that may collect physiological or environmental data. Such information complements social network studies and may allow for a deeper understanding of animal ecology and social behavior.
Tooth wear patterns in black rats (Rattus rattus) of Madagascar differ more in relation to human impact than to differences in natural habitats
Authors: Winkler Daniela E. , Andrianasolo Tolona H. , Andriamandimbiarisoa Laza , Ganzhorn Jörg U. , Rakotondranary S. Jacques , Kaiser Thomas M. , Schulz‐Kornas Ellen 
Published: March 2016

AbstractDietary characteristics and environmental variables are important selective factors directing ecological diversification in rodents. On Madagascar, the introductions and spread of the commensal black rat (Rattus rattus) can be seen as example cases to study dietary niche occupation and dietary adaptation in an insular environment. We investigate how tooth wear as a measure of dietary adaptation of black rats differs between four distinct habitats (village, manioc fields, spiny forest, and rainforest) with different dietary resources. We use the 3D surface texture analysis (3DST, using 30 parameters according to ISO 25178) as a measure of dietary abrasiveness. 3DST is applied on the occlusal surface of the upper first molar of 37 black rat specimens. The rainforest sample displays less rough and less voluminous surface textures compared to the village samples as indicated by smaller values for height parameters (Sa, Sp, Sq), inverse areal material ratio (Smc), and volume parameters (Vm, Vmc, Vmp, Vv, and Vvc). We therefore rank sampling areas from highest to lowest abrasiveness (village>manioc fields/spiny forest>rainforest). The rats from villages and rainforest differ to such an extent that one could have interpreted them to belong to different species. This indicates a high degree of variability in terms of ingesta abrasiveness. Furthermore, the pronounced difference between rats from human habitations compared to rats from associated fields or natural vegetation is interpreted to clearly indicate shifts in dietary niche occupation in relation to human impact.
The temporal scale of diet and dietary proxies
Authors: Davis Matt , Pineda‐Munoz Silvia 
Published: March 2016

AbstractDiets estimated from different proxies such as stable isotopes, stomach contents, and dental microwear often disagree, leading to nominally well‐supported but greatly differing estimates of diet for both extinct and extant species that complicate our understanding of ecology. We show that these perceived incongruences can be caused by proxies recording diet over vastly different timescales. Field observations reveal a diet averaged over minutes or hours, whereas dental morphology may reflect the diet of a lineage over millions of years of evolution. Failing to explicitly consider the scale of proxies and the potentially large temporal variability in diet can cause erroneous predictions in any downstream analyses such as conservation planning or paleohabitat reconstructions. We propose a cross‐scale framework for conceptualizing diet suitable for both modern ecologists and paleontologists and provide recommendations for any studies involving dietary data. Treating diet in this temporally explicit framework and matching the scale of our questions with the scale of our data will lead to a much richer and clearer understanding of ecological and evolutionary processes.
Fasciola hepatica tegumental antigens induce anergic‐like T cells via dendritic cells in a mannose receptor‐dependent manner
Authors: Aldridge Allison , O'Neill Sandra M. 
Published: March 2016

FoxP3+ Treg cells and anergic T cells are the two regulatory phenotypes of T‐cell responses associated with helminth infection. Here, we examine the T‐cell responses in mice during Fasciola hepatica infection, and to its tegumental coat antigens (FhTeg) that are shed from the fluke every 2–3 h. FhTeg comprises a rich source of glycoproteins, mainly oligomannose N‐glycans that bind to mannose receptor. This study demonstrated a novel mechanism for the T‐cell unresponsiveness observed during F. hepatica infection and after injection with FhTeg. Markers of T‐cell anergy, such as GRAIL, EGR2, ICOS, and ITCH, are enhanced amongst CD4+ T‐cell populations during infection and following FhTeg injection. This is characterized by a lack of cytokine responses and reduced proliferative activity, which can be reversed with the addition of IL‐2. FhTeg‐activated dendritic cells (DCs) suppress T cells in vitro as measured by enhanced GRAIL and CTLA4 by RNA and suppressed cytokine expression in anti‐CD3 stimulated CD4+ T cells. FhTeg‐treated DCs have enhanced MR expression, which is critical for DC‐CD4+ T‐cell communication. Taken together, this study presents markers of anergy in a mouse model of F. hepatica infection, and improves our understanding of host–pathogen interactions and how helminths modulate host immunity.
Organotemplate‐Free Synthesis of a High‐Silica Zeolite with a TON Structure in the Absence of Zeolite Seeds
Authors: Yeqing Wang  , Zhu Chenqi , Qiu Jing , Jiang Fan , Meng Xiangju , Wang Xiong , Lei Chi , Jin Yinying , Pan Shuxiang , Xiao Feng‐Shou 
Published: March 2016

AbstractA high‐silica zeolite with a TON structure designated as ZJM‐4 was successfully synthesized in the absence of any organic templates and zeolite seeds. Many factors such as the SiO2/K2O ratio, Si/Al ratio, SiO2/H2O in the starting aluminosilicate gels, crystallization temperature, and crystallization time strongly influence the formation of the ZJM‐4 zeolite. Interestingly, this synthesis shows very efficient silica utilization in the starting gels (>80 %). Catalytic tests on the isomerization of m‐xylene to p‐xylene show that the ZJM‐4 catalyst has high selectivity to p‐xylene (ca. 80 %), which could be potentially important for industrial applications for the ZJM‐4 zeolite as a candidate catalyst in the future.