bluuebunny/crossref_metadata_2025 huggingface dataset:
Structure and evolution of Alanine/Serine Decarboxylases and the engineering of theanine production
Authors: Wang Hao , Zhu Biying , Qiao Siming , Dong Chunxia , Wan Xiaochun , Gong Weimin , Zhang Zhaoliang
Published: August 2024

Ethylamine (EA), the precursor of theanine biosynthesis, is synthesized from alanine decarboxylation by alanine decarboxylase (AlaDC) in tea plants. AlaDC evolves from serine decarboxylase (SerDC) through neofunctionalization and has lower catalytic activity. However, lacking structure information hinders the understanding of the evolution of substrate specificity and catalytic activity. In this study, we solved the X-ray crystal structures of AlaDC from
Camellia sinensis
(CsAlaDC) and SerDC from
Arabidopsis thaliana
(AtSerDC). Tyr
341
of AtSerDC or the corresponding Tyr
336
of CsAlaDC is essential for their enzymatic activity. Tyr
111
of AtSerDC and the corresponding Phe
106
of CsAlaDC determine their substrate specificity. Both CsAlaDC and AtSerDC have a distinctive zinc finger and have not been identified in any other Group II PLP-dependent amino acid decarboxylases. Based on the structural comparisons, we conducted mutation screen of CsAlaDC. The results indicated that the mutation of L110F or P114A in the CsAlaDC dimerization interface significantly improved the catalytic activity by 110% and 59%, respectively. Combining a double mutant of CsAlaDC
L110F/P114A
with theanine synthetase increased theanine production 672% in an
in vitro
system. This study provides the structural basis for the substrate selectivity and catalytic activity of CsAlaDC and AtSerDC and provides a route to more efficient biosynthesis of theanine.
Glial ferritin maintains neural stem cells via transporting iron required for self-renewal in Drosophila
Authors: Ma Zhixin , Wang Wenshu , Yang Xiaojing , Rui Menglong , Wang Su
Published: August 2024

Stem cell niche is critical for regulating the behavior of stem cells. Drosophila neural stem cells (Neuroblasts, NBs) are encased by glial niche cells closely, but it still remains unclear whether glial niche cells can regulate the self-renewal and differentiation of NBs. Here we show that ferritin produced by glia, cooperates with Zip13 to transport iron into NBs for the energy production, which is essential to the self-renewal and proliferation of NBs. The knockdown of glial ferritin encoding genes causes energy shortage in NBs via downregulating aconitase activity and NAD
+
level, which leads to the low proliferation and premature differentiation of NBs mediated by Prospero entering nuclei. More importantly, ferritin is a potential target for tumor suppression. In addition, the level of glial ferritin production is affected by the status of NBs, establishing a bicellular iron homeostasis. In this study, we demonstrate that glial cells are indispensable to maintain the self-renewal of NBs, unveiling a novel role of the NB glial niche during brain development.
Characterization of indigenous Durio species from Sarawak, Borneo: relationships between chemical composition and sensory attributes
Authors: Sujang Gerevieve Bangi , Ramaiya Shiamala Devi , Lee Shiou Yih , Zakaria Muta Harah
Published: August 2024

Sarawak, Borneo, harbours 16 unique Durio species, half of which are edible, with only Durio zibethinus widely cultivated. Despite their nutritional and economic significance to the rural communities in Sarawak, the lesser-known indigenous durians remain underrepresented in the scientific literature while facing the risk of extinction in the wild. Thus, the aim of this study was to conduct comprehensive chemical analyses of these wild edible durians, offering insights into their nutritional and sensory taste attributes. The edible part was separated at optimal ripeness, and the samples were subjected to further analysis. Wild edible durian genotypes exhibit varied characteristics, even within the same species. The majority of wild durians are characterized by a sugar composition consisting predominantly of sucrose, constituting 67.38–96.96%, except for the red-fleshed Durio graveolens renowned for its low total sugar content (0.49 ± 0.17 g per 100 g). Despite its bland taste, this species possessed significantly greater fat (14.50 ± 0.16%) and fibre (12.30 ± 0.14%) content. Durio dulcis exhibited a significantly greater carbohydrate content (29.37–30.60%), and its intense smell was attributed to its low protein content (2.03–2.04%). Indigenous durians offer substantial percentages of daily mineral intake, with 100 g servings providing approximately 15.71–26.80% of potassium, 71.72–86.52% of phosphorus, 9.33–27.31% of magnesium, and sufficient trace minerals. The vibrant flesh colours of yellow-, orange- and red-fleshed Durio graveolens and Durio kutejensis show high levels of ascorbic acid (31.41–61.56 mg 100 g−1), carotenoids (976.36–2627.18 µg 100 g−1) and antioxidant properties, while Durio dulcis and Durio oxleyanus, despite their dull flesh, contained high phenolic (67.95–74.77 mg GAE 100 g−1) and flavonoid (8.71–13.81 QE mg 100 g−1) levels. These endeavours provide a deeper understanding of the nutritional richness of wild edible durians, thereby supporting commercialization and conservation efforts.
Heat Transfer and Performance Analysis of NaMgH2F-based Thermochemical Energy Storage System
Authors: Dubey Sumeet Kumar , Kumar K. Ravi , Tiwari Vinay , Srivastva Umish
Published: August 2024

Thermochemical energy storage systems are more suitable for high-temperature energy storage because of thermal stability and high energy storage density. Magnesium (Mg) based metal alloys and hydrides are found more suitable for high temperature energy storage applications among metal hydride-based thermochemical systems. The unit weight of NaMgH2F is used to analyze the energy sorption and heat transfer phenomenon. Initial metal hydride bed temperature variation and two heat transfer fluid flow arrangements are compared to study the heat transfer phenomenon and performance characteristics. The two initial metal hydride bed temperatures used in the analysis are 773 K and 823 K. Heat transfer flow Configuration 1 has axial tubes in the cross-section, while Configuration 2 has a circumferential fluid jacket along with the axial tubes. Both configurations have the same heat transfer area for the comparative study of heat transfer. The energy absorption was not affected significantly, but the energy desorption increased with an increase in metal hydride bed temperature and with the outer circumferential cooling jacket configuration. The energy storage efficiency of 93.2% and 94.4% is obtained for initial metal hydride bed temperatures of 773 K and 823 K with flow configuration 1, while the energy storage efficiency of 95.2% and 96.4% is obtained for 773 K and 823 K with flow Configuration 2.
Nutritional Potential of the Caterpillar Imbrasia obscura (Butler, 1878) Consumed in the Kara Region of Togo
Authors: Badanaro Fègbawè , Mélila Mamatchi
Published: August 2024

Lepidopteran larvae, which constitute unconventional food resources in many parts of the world, are consumed by aboriginal populations in Togo without any study being carried out on their nutritional value. The aim of this study was to assess the nutritional composition of the caterpillar Imbrasia obscura (Butler, 1878) consumed by populations in the Kara Region of Togo. To this end, 9 I. obscura samples were taken from three localities in this region.  Ash, protein, vitamin and lipid contents were determined using AOAC (Association of Official Analytical Chemists) method, and fiber content using the AFNOR (Association française de normalization) method. Minerals were analyzed spectrophotometrically and colorimetrically. The fatty acid composition was determined by chromatography. The result of this research showed that I. obscura contain 10.41 ± 0.33 % moisture, 53.36 ± 0.05 % protein, 14.22 ± 0.62% lipids, 10.67 ± 0.62 % fiber and 1.04 ± 0.54 % carbohydrates. Lipids contain monounsaturated (oleic (30.57 ± 0.03 %) and elaidic (0.46 ± 0.02 %) acids) and polyunsaturated fatty acids (linoleic (4.82 ± 0.02 %), α-linolenic (1.872 ± 0.02 %), γ-linolenic (1.57 ± 0.01 %) and arachidonic (2.33 ± 0.01 %) acids). With regard to micronutrient composition, the average mineral content is 10.3 % and varies according to the nature of each mineral. I. obscura also contains variable levels of fat-soluble vitamins (retinol: 0.02 ± 0.01 mg/100g and tocopherol 4.10 ± 0.07 mg/100g) and water-soluble vitamins (thiamine: 1.35 ± 0.16 mg/100g, riboflavin: 2.12 ± 0.11 mg/100g and niacin: 4.10 ± 0.07 mg/100g). These data show the quantitative and qualitative richness of I. obscura in nutrients. This species could therefore contribute to the nutritional balance of consumers and deserves to be given greater prominence on our plates.
Nutritional Quality, Phytochemical and Mineral Assessment from Various Accessions of Bambara Groundnut
Authors: Zulkhairi A. Mohd , Fazlyzan A. , Izar K. Maya , Shafie M.S. Muhammad , Asiah I. Nor , Aisyah M.N. Siti , Aqilah M.Y. Saidatul , Daliana Y. Nur
Published: August 2024

Aims: To evaluate nutritional composition, polyphenols contents and antioxidant activity from various accessions of Bambara groundnut (BGN) (Vigna subterranea) in Malaysia.
Study Design:  Different parts of BGN were extracted and investigated for its nutritional composition, total p0068enolic contents (TPC) and free radical scavenging testing. Each sample were extracted in triplicates (n=3). Tabulated data were statistically analyzed using Duncan's Multiple Range Test (DMRT).
Place and Duration of Study: Herbarium and Phytochemistry Laboratory. Agrobiodiversity and Environment Research Centre (Kompleks MyGene Bank), MARDI, Serdang, Malaysia from November 2023 to February 2024.
Methodology: Four accessions of BGN (BGN996, BGN997, BGN998 and BGN999) were morphologically characterized and determine its proximate and minerals composition while different parts (seed, pod and testa) from each of the accessions were extracted to evaluate its polyphenols content and antioxidant activity.
Results: The nutritional analysis revealed significant variations in carbohydrate, protein, and energy content among the accessions. BGN 999 exhibited the highest carbohydrate (65.2 g/100g) and energy contents (403.7 kcal/100g), while BGN 997 had the highest protein content (22.6 g/100g). Analysis of mineral composition showed potassium as the predominant mineral, with contents ranging from 1552.7 to 1712.3 mg/100g, surpassing other essential minerals like phosphorus, magnesium, and zinc. Meanwhile, extracts from the different parts of BGN (seed, pod and testa) from all of the accessions were subjected to the TPC and antioxidant testing. The TPC analysis showed significant differences in phenolic contents across different BGN parts, with the testa exhibiting the highest TPC (45.02 to 56.78 g GAE/100g DW). The free radical scavenging assay revealed that BGN 996 had the strongest antioxidant activity among the testas, with the lowest IC50 value (0.37 mg/ml).
Conclusion: This study underscores the nutritional and antioxidant potential of Bambara groundnut, highlighting its role as a functional food rich in phenolic compounds and essential nutrients beneficial for human health. Future research should further explore its applications in both the food and nutraceutical industries, leveraging its promising attributes for enhanced dietary and health benefits.
Impact of Illegal Anthropogenic Activities on the Spatio-temporal Variations in the Distribution of the Defassa Waterbuck Population (Kobus ellipsiprymnus defassa, Rüppel, 1835) in the Classified Forest and Game Ranch of Nazinga, Burkina Faso
Authors: Roland Konate Sidiki , Ardjima Lankoande , Djidama Sirima , Théophile Dibloni Ollo , Kevin Tiendrebeogo , Emmanuel Hema Midibahaye
Published: August 2024

The number of defassa waterbuck populations in the Nazinga Classified Forest and Game Ranch is declining. Few studies have been carried out on the distribution of this population. In general, the defassa waterbuck populations as well as other mammals are subject to abusive exploitation linked to anthropogenic activities. This study was to evaluate the influence of anthropogenic activities on the distribution of the defassa waterbuck population in the Nazinga Classified Forest after fourteen years (2006-2019) of collection. For this, the line transect method was used for the census of fauna and indices of the presence of anthropogenic activities. Thus, from these data, the numbers varied from 2434 individuals [95% CI (1074-5512)] in 2006 to 646 individuals [95% CI (292-1430)] in 2019 and the densities of 0.71 [95% CI (0.32) -1.57)] in 2019 to 2.67 [95% CI (1.18-6.04)] in 2006. This population remained a group from 2006 to 2019 in the conservation zone integral in search of tranquility. Indices of poaching, human presence and livestock significantly influence the numbers of this population over time. The results obtained will make it possible to develop the conservation and management plan for hunting resources aimed at preserving the wildlife diversity of the Ranch.
Sources and fate of polycyclic aromatic hydrocarbons in the Antarctic and Southern Ocean atmosphere
Authors: Cabrerizo Ana , Galbán‐Malagón Cristóbal , Del Vento Sabino , Dachs Jordi
Published: November 2014

Polycyclic aromatic hydrocarbons (PAHs) are a geochemically relevant family of semivolatile compounds originating from fossil fuels, biomass burning, and their incomplete combustion, as well as biogenic sources. Even though PAHs are ubiquitous in the environment, there are no previous studies of their occurrence in the Southern Ocean and Antarctic atmosphere. Here we show the gas and aerosol phase PAHs concentrations obtained from three sampling cruises in the Southern Ocean (Weddell, Bellingshausen, and South Scotia Seas), and two sampling campaigns at Livingston Island (Southern Shetlands). This study shows an important variability of the atmospheric concentrations with higher concentrations in the South Scotia and northern Weddell Seas than in the Bellingshausen Sea. The assessment of the gas‐particle partitioning of PAHs suggests that aerosol elemental carbon contribution is modest due to its low concentrations. Over the ocean, the atmospheric concentrations do not show a temperature dependence, which is consistent with an important role of long‐range atmospheric transport of PAHs. Conversely, over land at Livingston Island, the PAHs gas phase concentrations increase when the temperature increases, consistently with the presence of local diffusive sources. The use of fugacity samplers allowed the determination of the air‐soil and air‐snow fugacity ratios of PAHs showing that there is a significant volatilization of lighter molecular weight PAHs from soil and snow during the austral summer. The higher volatilization, observed in correspondence of sites where the organic matter content in soil is higher, suggests that there may be a biogenic source of some PAHs. The volatilization of PAHs from soil and snow is sufficient to support the atmospheric occurrence of PAHs over land but may have a modest regional influence on the atmospheric occurrence of PAHs over the Southern Ocean.
Lunar gravitational atmospheric tide, surface to 50 km in a global, gridded data set
Authors: Kohyama Tsubasa , Wallace John M.
Published: November 2014

The lunar gravitational semidiurnal atmospheric tide L2 is detected in the geopotential field in the ERA‐Interim reanalysis by regressing the data for each of the four daily analysis times onto periodic lunar half‐synodic cycle time series and differencing the resulting regression maps. A robust pattern dominated by zonal wave number 2 emerges, which agrees with tidal theory and with previous observational studies based on station data in terms of its amplitude, phase, and seasonality at the Earth's surface. Above the 100 hPa level, the tidal signal amplifies with height and it is downward propagating; below that level it is almost barotropic. The L2 signal is resolvable even in data for individual months of individual years. Monthly time series of tidal amplitude and phase exhibit a well‐defined pattern of seasonality year after year. Since the ERA forecast model has no L2 gravitational forcing, the source of its L2 signal must be in the observations.
Seasonal variability of the warm Atlantic water layer in the vicinity of the Greenland shelf break
Authors: Grist Jeremy P. , Josey Simon A. , Boehme Lars , Meredith Michael P. , Laidre Kristin L. , Heide‐Jørgensen Mads Peter , Kovacs Kit M. , Lydersen Christian , Davidson Fraser J. M. , Stenson Garry B. , Hammill Mike O. , Marsh Robert , Coward Andrew C.
Published: November 2014

The warmest water reaching the east and west coast of Greenland is found between 200 and 600 m. While important for melting Greenland's outlet glaciers, limited winter observations of this layer prohibit determination of its seasonality. To address this, temperature data from Argo profiling floats, a range of sources within the World Ocean Database, and unprecedented coverage from marine‐mammal borne sensors have been analyzed for the period 2002–2011. A significant seasonal range in temperature (~1‐2°C) is found in the warm layer, in contrast to most of the surrounding ocean. The phase of the seasonal cycle exhibits considerable spatial variability, with the warmest water found near the eastern and southwestern shelf break toward the end of the calendar year. High‐resolution ocean model trajectory analysis suggests the timing of the arrival of the year's warmest water is a function of advection time from the subduction site in the Irminger Basin.
ImprovedBayesian multimodeling: Integration of copulas andBayesian model averaging
Authors: Madadgar Shahrbanou , Moradkhani Hamid
Published: November 2014

Bayesian model averaging (BMA) is a popular approach to combine hydrologic forecasts from individual models and characterize the uncertainty induced by model structure. In the original form of BMA, the conditional probability density function (PDF) of each model is assumed to be a particular probability distribution (e.g., Gaussian, gamma, etc.). If the predictions of any hydrologic model do not follow certain distribution, a data transformation procedure is required prior to model averaging. Moreover, it is strongly recommended to apply BMA on unbiased forecasts, whereas it is sometimes difficult to effectively remove bias from the predictions of complex hydrologic models. To overcome these limitations, we develop an approach to integrate a group of multivariate functions, the so‐called copula functions, into BMA. Here we introduce a copula‐embedded BMA (Cop‐BMA) method that relaxes any assumption on the shape of conditional PDFs. Copula functions have a flexible structure and do not restrict the shape of posterior distributions. Furthermore, copulas are effective tools in removing bias from hydrologic forecasts. To compare the performance of BMA with Cop‐BMA, they are applied to hydrologic forecasts from different rainfall‐runoff and land‐surface models. We consider the streamflow observation and simulations for 10 river basins provided by the Model Parameter Estimation Experiment (MOPEX) project. Results demonstrate that the predictive distributions are more accurate and reliable, less biased, and more confident with small uncertainty after Cop‐BMA application. It is also shown that the postprocessed forecasts have better correlation with observation after Cop‐BMA application.
Controlling the Dynamics of Cell Transition in Heterogeneous Cultures using Surface Chemistry
Authors: Hickman Graham J. , Rees Robert C. , Boocock David J. , Pockley A. Graham , Perry Carole C.
Published: November 2014

Developing materials that can preferentially select defined cancer cell populations for biological characterization will greatly enhance our understanding of cancer cell growth, differentiation, and invasion. The transitional events between epithelial and mesenchymal phenotypes are particularly crucial, as primary tumors and secondary metastasis are generally epithelial in nature, whereas circulating mesenchymal cells derived from primary epithelial cells appear to facilitate the spread of disease and its resistance to therapy. This study describes an amino‐functionalized material, which promotes the enrichment of an epithelial phenotype from a single cell line containing both epithelial and mesenchymal subpopulations of cancer cells. The isolation and transitional control of such subpopulations using functional materials will advance understanding of the disease process, have a significant impact on the downstream development of new targeted cancer therapeutics, and also be applicable to tissue engineering and regenerative medicine.
Development and Evaluations of Aceclofenac Microcapsules for Colon‐Targeted Delivery: An In Vitro Study
Authors: Farooq Muhammad , Ahmad Mahmood , Madni Asadullah , Hanif Muhammad , Khan Muhammad Rizwan
Published: November 2014

Microcapsules of aceclofenac with pH‐dependent release properties for achieving targeted delivery to colon were developed. A solvent evaporation technique was adopted for microcapsules preparation using Eudragit RS 100 as a retardant polymer. The microcapsules were found free flowing, whitish, and spherical in shape. The entrapment efficacies of microcapsules were 95.73, 85.67, and 84% for F1 (1:1), F2 (1:2), and F3 (1:3), respectively. The particle size was in the range of 12 ± 2.48 to 32 ± 2.20 μm. The X‐ray diffraction and Fourier transforms infrared (FTIR) studies of prepared microcapsules illustrated that there was no interaction between drug and polymer. The dissolution performed in three different pH media (1.2, 6.8, and 7.4) at 37 ± 0.5°C elucidates negligible release at pH 1.2 for 2 h but changing the pH from 1.2 to 6.8, showed burst release after 4 h and then demonstrated a constant release rate at 7.4 pH. The time for half‐life of microcapsules showed that drug release from F1 microcapsules was quicker than F2 and F3. The time for half‐life of capsule filled microcapsules was 15.54, 17.40, and 20.08 h, respectively. The formulated microcapsules do not show the release in gastric medium but released at phosphate buffer pH 6.8 and 7.4.
Origins of marronage: Mitochondrial lineages ofJamaica'sAccompongTownMaroons
Authors: Madrilejo Nicole , Lombard Holden , Torres Jada Benn
Published: November 2014

Objectives

The Accompong Town Maroons are descendants of enslaved Africans who successfully waged war against British colonial rule and established an independent community in western Jamaica. There are discrepancies regarding Accompong Town Maroon ancestry with some scholars noting ancestry from both Africans and Taínos, Jamaica's indigenous population, while other scholars only acknowledge African ancestry. We considered the mitochondrial lineages of contemporary Accompong Town Maroons to address the question of ancestral origins.

Methods

We sequenced a section of the mitochondrial DNA control region (np 16,024–16,569) and genotyped a panel of hierarchically selected haplogroup diagnostic SNPs for 50 individuals with genealogical ties to Accompong Town. Mitochondrial haplotypes were also compared with publically available Jamaican mitochondrial haplotypes using an exact test as well as haplotypes within the EMPOP public database to further access biogeographic origins.

Results

L‐type mitochondrial haplogroups were observed in 96% of samples, and the remaining 4% belonged to haplogroup B2. Haplotype diversity was 0.922 (SD = 0.024) and not significantly different than the comparable Jamaican population. Of the two B2 haplotypes, one matched haplotypes throughout the Americas and East Asia and the other matched only in East Asia. These results suggest both African and indigenous American maternal ancestries within Accompong Town.

Conclusions

Our data suggested that the maternal ancestry of contemporary Accompong Town Maroons is predominantly African and, despite claims to suggest otherwise, also indigenous American. Our study complemented Maroon oral histories, archeological data, and illuminated how colonization shaped human genetic variation within the Caribbean. Am. J. Hum. Biol. 27:432–437, 2015. © 2014 Wiley Periodicals, Inc.
Dreidimensionale Tomographie im mittleren Infrarotbereich von endogenen und exogenen Molekülen in einer einzelnen Zelle mit subzellulärer Auflösung
Authors: Quaroni Luca , Obst Martin , Nowak Marcus , Zobi Fabio
Published: November 2014

Mikroskopie im mittleren infraroten Spektralbereich liefert detaillierte chemische Informationen über eine Probe bei moderater Ortsauflösung und wird daher immer häufiger für die Charakterisierung von biologischen Proben wie etwa einzelnen Zellen verwendet. Aufgrund der Komplexität der Probentopographie sind konventionelle 2D‐Bildgebungen jedoch in ihren Möglichkeiten limitiert, spezifische Informationen zur Probenzusammensetzung mit subzellulären Strukturen in Verbindung zu bringen. Wir stellen hier eine Methode und detaillierte Versuchsbeschreibungen vor, welche es ermöglichen, diese Einschränkungen durch Kippserientomographie mit einem konventionellen Infrarot‐Labormikroskop zu umgehen. Basierend auf dem intrinsischen IR‐Absorptionskontrast ermöglicht dieser Ansatz, quantitative 3D‐Verteilungen von molekularen Komponenten zu erstellen. Wir demonstrieren die Methode anhand der Quantifizierung der Verteilung eines exogenen Metallcarbonyl‐Komplexes innerhalb einer Zelle sowie durch die Darstellung der Veränderungen der Koordinationsumgebung des Komplexes in verschiedenen Zellkompartimenten.
The Catalytic Asymmetric Abramov Reaction
Authors: Guin Joyram , Wang Qinggang , van Gemmeren Manuel , List Benjamin
Published: November 2014

The first catalytic enantioselective Abramov reaction is described. The process is based on the utilization of a chiral disulfonimide catalyst, which efficiently avoids the difficulties encountered with metal‐based catalysts. Several functionalized α‐hydroxy phosphonates were synthesized in good yields and with excellent enantiomeric ratios of up to >99:1. The process was shown to be scalable and up to 1 g of starting material could be employed under mild reaction conditions.
Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics
Authors: Brus Jiří , Kobera Libor , Schoefberger Wolfgang , Urbanová Martina , Klein Petr , Sazama Petr , Tabor Edyta , Sklenak Stepan , Fishchuk Anna V. , Dědeček Jiří
Published: November 2014

Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework AlFR Lewis acid sites are often found in their H‐forms. The formation of AlFR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of AlFR Lewis sites in dehydrated zeolites and their precursors—“perturbed” AlFR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)3AlOH groups and are characterized by a broad 27Al NMR resonance (δi=59–62 ppm, CQ=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the 27Al MAS NMR spectrum. Dehydroxylation of (SiO)3AlOH occurs at mild temperatures and leads to the formation of AlFR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)3Al Lewis sites exhibit an extremely broad 27Al NMR resonance (δi≈67 ppm, CQ≈20 MHz, and η≈0.1).
Synthesis of nanostructure hydroxy sodalite composite membranes via hydrothermal method: support surface modification and synthesis method effects
Authors: Kalantari Neda , Vaezi Mohammad Javad , Yadollahi Mostafa , Babaluo Ali Akbar , Bayati Behruz , Kazemzadeh Akram
Published: November 2014

Multilayer hydroxy sodalite zeolite membranes were synthesized on the outer surface of support with and without modification via in situ and secondary growth hydrothermal synthesis methods. The synthesized zeolite membranes were characterized by X‐ray diffraction, scanning electron microscopy, and single gas (H2, N2, and n‐pentane) permeation measurements at different pressure differences. The membranes synthesized by secondary growth method on the modified support were found to be highly intergrown, but the permeation results for hydrogen and n‐pentane at a temperature of 323 K were not repeatable, which can be related to the weak interaction between zeolite layer and substrate. High performance hydroxy sodalite zeolite membrane was successfully formed on a nonmodified α‐Al2O3 support by in situ hydrothermal synthesis method. No permeance of n‐pentane was measured for this membrane at 323 K and 2 bar so that infinite permselectivity of H2/n‐C5H12 could be obtained for the four‐layer synthesized membrane on the nonmodified support, verifying the synthesis of a good quality hydroxy sodalite zeolite membrane. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Hybrid biomimetic electrospun fibrous mats derived from poly(ε‐caprolactone) and silk fibroin protein for wound dressing application
Authors: Chutipakdeevong Jesada , Ruktanonchai Uracha , Supaphol Pitt
Published: November 2014

To achieve excellent biofunctionality of Bombyx mori silk fibroin (SF), we explored a novel hybridization method to combine the unique properties of SF with poly(ε‐caprolactone) (PCL) electrospun fibers. The hybrid electrospun fibers demonstrate excellent hydrophilicity and biocompatibility that are important to tissue engineering applications. The biomimetic fibrous structure was fabricated by conventional electrospinning of PCL. The individual surfaces of PCL electrospun fibers were coated with silk fibroin protein using a lyophilization technique. The SF coating layers were durable which were further developed by surface modification with fibronectin to improve their biological function. The hybrid electrospun fibers show excellent support for normal human dermal fibroblast (NHDF) cells adhesion and proliferation than neat PCL fibers, while the surface‐modified hybrid electrospun fibers show significantly enhanced proliferation of NHDF cells on their surface. This study indicates the new opportunity of fabrication technique that can construct a biomimetic fibrous structure while the original function as a biomaterial remained existing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41653.
Marine protected areas management in the Caribbean and Mediterranean seas: making them more than paper parks
Authors: Bustamante Georgina , Canals Purificación , Di Carlo Giuseppe , Gomei Marina , Romani Marie , Souan Helene , Vanzella‐Khouri Alessandra
Published: November 2014

The paper comprises recommendations presented and discussed at several workshops of the 3rd International Marine Protected Areas Congress (Marseille, France, 21–27, October, 2013) to achieve effective management of marine protected areas in the Caribbean and Mediterranean Seas.

It highlights the similarities but also differences between the two areas as a result of their distinct biogeographic and cultural characteristics.

The biophysical setting, socioeconomic scenario and issues related to marine protected areas in the Caribbean and Mediterranean Seas are summarized and case studies from both regions are presented that illustrate the level of success thus far achieved by MPAs.

Factors contributing to MPA success are related to ecological conditions, the involvement of stakeholders in decision‐making processes, and to better governance, as well as improved communication and training.

The SPAW and SPA regional environmental agreements administered by the UNEP Regional Seas Programmes in collaboration with government and non‐government partners and the MPA managers' networks have provided technical assistance that has led to improved management.

The experience of the last 3 years of contacts between both regional networks of MPA scientists and practitioners (i.e. MedPAN and CaMPAM) highlights the benefits of such an initiative and suggests the need to develop a robust transoceanic Exchange Programme to facilitate knowledge transfer.

Copyright © 2014 John Wiley & Sons, Ltd.
Governance challenges in scaling up from individual MPAs to MPA networks
Authors: Solandt Jean‐Luc , Jones Peter , Duval‐Diop Dominique , Kleiven Alf Ring , Frangoudes Katia
Published: November 2014

With the drive for greater numbers and areas of MPAs to be put in place to meet national and international targets, challenges have emerged in both the establishment and development of sustainable governance of the networks of sites that are emerging.

Using 12 presentations given in a workshop on ‘Improving participation for better governance of MPAs’ at the 3rd International Marine Protected Areas Congress in October 2013, this paper reviews a range of top‐down, bottom‐up and collaborative approaches to governance, looking at all phases in the process from design of an MPA network to its implementation, as well as considering individual MPAs.

Designation of MPA networks requires significant investment of resources to engage local stakeholders in discussions over potential site location and management measures.

Scaling‐up from individual MPAs to networks of MPAs will often also require a scaling‐up of governance approaches, including top‐down approaches.

Balancing the need to provide for the participation of local users in each constituent MPA with the need to address a variety of challenges, whilst achieving wider‐scale objectives through the inclusion of top‐down governance approaches is an important but neglected challenge in discussions concerning MPA networks.

These case studies indicate that there are various ways in which this challenge can be addressed in different contexts and point to potential ‘good practice’ for other MPAs in similar scenarios.

Copyright © 2014 John Wiley & Sons, Ltd.
A Chemoenzymatic and Fully Stereocontrolled Total Synthesis of the Antibacterial Natural Product (−)‐Platencin
Authors: Chang Ee Ling , Schwartz Brett D. , Draffan Alistair G. , Banwell Martin G. , Willis Anthony C.
Published: November 2014

The natural product (−)‐platencin is a potent antibacterial agent that exerts its effects through a novel mode of action. As such, it is an important lead in the development of next‐generation antibacterials that are urgently needed because of the rapidly developing resistance to current therapies. The work reported here concerns the development of a convergent and chemoenzymatic total synthesis of (−)‐platencin by methods that should provide access to a range of biologically relevant analogues. The key step involves a thermally promoted and facially selective intramolecular Diels–Alder (IMDA) cycloaddition reaction to give an adduct that embodies the tricarbocyclic core of (−)‐platencin. This adduct was elaborated over thirteen steps to the natural product. The substrate for the IMDA reaction was prepared by Stille cross‐coupling of a Z‐configured alkenylstannane with an iodinated diene obtained in an enantiomerically pure form through the whole‐cell biotransformation of iodobenzene.
A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media
Authors: Cornut Damien , Moerkerke Steven , Wouters Johan , Bruylants Gilles , Jabin Ivan
Published: November 2014

The efficient synthesis of calix[6]cryptothiourea 6 was achieved through a two‐step sequence that involves a key [1+1] macrocyclization step. It was shown by NMR spectroscopy that this heteroditopic receptor can bind zwitterions in protic media with an outstanding selectivity for β‐alanine betaine G5, which is likely due to a high complementarity between the two partners. This result constitutes a rare example of cavity complexation of a zwitterion by a calix[6]arene. In comparison with the parent urea‐based receptors, 6 behaves as a much more efficient host for betaines. This strengthening of the binding properties is due to the better preorganization of the tripodal hydrogen‐bonding cap as well as to the higher acidity of the thiourea groups and their poor ability to self‐associate. Remarkably, host 6 is able to perform solid–liquid as well as liquid–liquid extraction of G5. Finally, 6 provides an excellent structural model for the binding site of glycine betaine G4 encountered in natural systems.
Copper‐Catalyzed Aerobic CC Bond Cleavage of Lactols with N‐Hydroxy Phthalimide for Synthesis of Lactones
Authors: Tnay Ya Lin , Chiba Shunsuke
Published: November 2014

The transformation of cyclic hemiacetals (lactols) into lactones has been achieved by Cu‐catalyzed aerobic CC bond cleavage in the presence of N‐hydroxy phthalimide (NHPI). The present process is composed of a multistep sequence including a) formation of exo‐cyclic enol ethers by dehydration; b) addition of phthalimide N‐oxyl radical to the enol ethers followed by trapping of the resulting C‐radicals with molecular oxygen to form peroxy radicals; c) reductive generation of oxy radicals and subsequent β‐radical fragmentation to generate lactones.
A multiple testing method for hypotheses structured in a directed acyclic graph
Authors: Meijer Rosa J. , Goeman Jelle J.
Published: November 2014

We present a novel multiple testing method for testing null hypotheses that are structured in a directed acyclic graph (DAG). The method is a top‐down method that strongly controls the familywise error rate and can be seen as a generalization of Meinshausen's procedure for tree‐structured hypotheses. Just as Meinshausen's procedure, our proposed method can be used to test for variable importance, only the corresponding variable clusters can be chosen more freely, because the method allows for multiple parent nodes and partially overlapping hypotheses. An important application of our method is in gene set analysis, in which one often wants to test multiple gene sets as well as individual genes for their association with a clinical outcome. By considering the genes and gene sets as nodes in a DAG, our method enables us to test both for significant gene sets as well as for significant individual genes within the same multiple testing procedure. The method will be illustrated by testing Gene Ontology terms for evidence of differential expression in a survival setting and is implemented in the package cherry.
Young Children's Difficulty with Indirect Speech Acts: Implications for Questioning Child Witnesses
Authors: Evans Angela D. , Stolzenberg Stacia N. , Lee Kang , Lyon Thomas D.
Published: November 2014

Prior research suggests that infelicitous choice of questions can significantly underestimate children's actual abilities, independently of suggestiveness. One possibly difficult question type is indirect speech acts such as “Do you know…” questions (DYK, e.g., “Do you know where it happened?”). These questions directly ask if respondents know, while indirectly asking what respondents know. If respondents answer “yes,” but fail to elaborate, they are either ignoring or failing to recognize the indirect question (known as pragmatic failure). Two studies examined the effect of indirect speech acts on maltreated and non‐maltreated 2‐ to 7‐year‐olds’ post‐event interview responses. Children were read a story and later interviewed using DYK and Wh‐ questions. Additionally, children completed a series of executive functioning tasks. Both studies revealed that using DYK questions increased the chances of pragmatic failure, particularly for younger children and those with lower inhibitory control skills. Copyright © 2014 John Wiley & Sons, Ltd.
N‐Heterocyclic Carbenes Supported on Vinylic Addition Polynorbornene: A Recyclable and Recoverable Organocatalyst
Authors: Molina de la Torre Jesús A. , Albéniz Ana C.
Published: November 2014

A bromoalkyl functionalized vinylic addition polynorbornene has been used as an inert new scaffold to support imidazolium salts by straightforward nucleophilic substitution using different imidazoles ImR (R=Me, mesityl, 2,6‐iPr2C6H3). These polymers, VA‐PNB‐(CH2)4ImRBr, are precursors of N‐heterocyclic carbenes which are useful as heterogeneous organocatalysts. The polymeric carbenes have been tested in two model reactions: The synthesis of saturated esters from α,β‐unsaturated aldehydes and the conjugate umpolung reaction of α,β‐unsaturated aldehydes for the synthesis of γ‐butyrolactones. The supported catalyst (R=mesityl) is fully recyclable and can be recovered as an imidazolium salt and stored for further use.
Deciphering Ligands’ Interaction with Cu and Cu2O Nanocrystal Surfaces by NMR Solution Tools
Authors: Glaria Arnaud , Cure Jérémy , Piettre Kilian , Coppel Yannick , Turrin Cédric‐Olivier , Chaudret Bruno , Fau Pierre
Published: November 2014

The hydrogenolysis of [Cu2{(iPrN)2(CCH3)}2] in the presence of hexadecylamine (HDA) or tetradecylphosphonic acid (TDPA) in toluene leads to 6–9 nm copper nanocrystals. Solution NMR spectroscopy has been used to describe the nanoparticle surface chemistry during the dynamic phenomenon of air oxidation. The ligands are organized as multilayered shells around the nanoparticles. The shell of ligands is controlled by both their intermolecular interactions and their bonding strength on the nanocrystals. Under ambient atmosphere, the oxidation rate of colloidal copper nanocrystals closely relies on the chemical nature of the employed ligands (base or acid). Primary amine molecules behave as soft ligands for Cu atoms, but are even more strongly coordinated on surface CuI sites, thus allowing a very efficient corrosion protection of the copper core. On the contrary, the TDPA ligands lead to a rapid oxidation rate of Cu nanoparticles and eventually to the re‐dissolution of CuII species at the expense of the nanocrystals.
Strong Interplay between the Electron Spin Lifetime in Chemically Synthesized Graphene Multilayers and Surface‐Bound Oxygen
Authors: Náfrádi Bálint , Choucair Mohammad , Southon Peter D. , Kepert Cameron J. , Forró László
Published: November 2014

The electron spin lifetime in an assembly of chemically synthesized graphene sheets was found to be extremely sensitive to oxygen. Introducing small concentrations of physisorbed O2 onto the graphene surface reduced the exceptionally long 140 ns electron spin lifetime by an order of magnitude. This effect was completely reversible: Removing the O2 by using a dynamic vacuum restored the spin lifetime. The presence of covalently bound oxygen also decreased the electron spin lifetime in graphene, although to a far lesser extent compared to physisorbed O2. The conduction electrons in graphene were found to play a significant role by counter‐balancing the spin depolarization caused by oxygen molecules. Our results highlight the importance of chemical environment control and device packing in practical graphene‐based spintronic applications.
Fluorination of Isotopically Labeled Turbostratic and Bernal Stacked Bilayer Graphene
Authors: Ek Weis Johan , Costa Sara D. , Frank Otakar , Bastl Zdenek , Kalbac Martin
Published: November 2014

Fluorination of graphene opens up a bandgap, which creates opportunities for optoelectronics, and also paves the way for the creation of extremely thin insulating layers, which can be important for applications in devices. However, in spite of many interesting features offered by, for example, unequally doped layers in multilayered systems, most of the work has concerned the fluorination of graphene monolayers. Here, the fluorination process of graphene bilayers is investigated through high‐resolution Raman mapping followed by analysis of more than 10 000 spectra of bilayer graphene. Isotopically labeled bilayers are used, allowing each individual layer in bilayer graphene to be addressed unambiguously. The fluorinated graphene is prepared through exposure to XeF2. Monolayer graphene is found to be significantly more sensitive to fluorination than bilayer graphene. Through comparison of the D/G area ratio and the position of the G band for turbostratic and Bernal stacked (AB) bilayers, it is found that the fluorination process is more effective for turbostratic than for AB‐stacked bilayer graphene. The fluorination changes the electronic structure similarly for the top and bottom layers in turbostratic bilayers. However, the top layer is more sensitive than the bottom layer in AB‐stacked bilayers.
ChemInform Abstract: High‐Throughput ab initio Screening for Two‐Dimensional Electride Materials.
Authors: Tada Tomofumi , Takemoto Seiji , Matsuishi Satoru , Hosono Hideo
Published: November 2014

High‐throughput ab initio electronic structure calculations of about 34000 materials in a screening platform are performed to identify two‐dimensional electride materials, which are composed of cationic layers and anionic electrons confined in a two‐dimensional empty space.
ChemInform Abstract: mP‐BaP3: A New Phase from an Old Binary System.
Authors: Dolyniuk Juli‐Anna , Kaseman Derrick C. , Sen Sabyasachi , Zhao Jing , Osterloh Frank E. , Kovnir Kirill
Published: November 2014

The new title phase is synthesized by solid state reaction of a stoichiometric mixture of the elements (carbonized silica ampule, 1073 K, 140 h) and characterized by single crystal XRD, UV/VIS diffuse reflectance spectroscopy, 31P solid state MAS NMR, surface photovoltage spectroscopy, and DFT band structure calculations.
ChemInform Abstract: Doping Effects of Group‐IIIA Elements on Physical Properties of ZnMgXO (X: Al, Ga, In, Tl) Transparent Conducting Oxide Films Prepared by RF Magnetron Sputtering.
Authors: Jeong Sang‐Hun , Park Jang‐Ho , Lee Byung‐Teak
Published: November 2014

Zn0.88Mg0.1M0.02O (M: Al, Ga, In, Tl) films are grown on quartz by radio‐frequency magnetron sputtering using ceramic targets prepared by cold isostatic pressing and sintering of the respective metal oxide powders (950 °C, 6 h).
ChemInform Abstract: Crystalline Li3V6O16 Rods as High‐Capacity Anode Materials for Aqueous Rechargeable Lithium Batteries (ARLB).
Authors: Nair Vivek Sahadevan , Sreejith Sivaramapanicker , Borah Parijat , Hartung Steffen , Bucher Nicolas , Zhao Yanli , Madhavi Srinivasan
Published: November 2014

Li3V6O16 rods are hydrothermally synthesized from aqueous mixtures of LiOAc and V2O5 (autoclave, 200 °C, 48 h), followed by heat treatment at 400 °C.
ChemInform Abstract: Polytopic Bis(oxazoline)‐Based Ligands for the Development of Recoverable Catalytic Systems Applied to the Cyclopropanation Reaction.
Authors: Garcia Jose I. , Garcia Jaime , Herrerias Clara I. , Mayoral Jose A. , Minana Ana C. , Saenz Carlos
Published: November 2014

Several polytopic ligands are synthesized and tested in this model reaction.
ChemInform Abstract: N,N‐Dimethylaminobenzoates Enable Highly Enantioselective Sharpless Dihydroxylations of 1,1‐Disubstituted Alkenes.
Authors: Zhao Yaohong , Xing Xiangyou , Zhang Shaolong , Wang David Zhigang
Published: November 2014

The N,N‐dimethylaminobenzoate moiety is found to be an efficient auxiliary for inducing high levels of enantioselectivity in the dihydroxylation of the challenging substrate class of 1,1‐disubstituted aliphatic alkenes (I) and (III).
ChemInform Abstract: Enantioselective Cascade Formal Reductive Insertion of Allylic Alcohols into the C(O)—C Bond of 1,3‐Diketones: Ready Access to Synthetically Valuable 3‐Alkylpentanol Units.
Authors: Roudier Mylene , Constantieux Thierry , Quintard Adrien , Rodriguez Jean
Published: November 2014

Functionalized γ‐chiral alcohols are prepared via an unprecedented cascade reaction which combines dual iron—amine‐catalyzed enantioselective functionalization of allylic alcohols and chemoselective acyl transfer.
ChemInform Abstract: Introducing Deep Eutectic Solvents to Polar Organometallic Chemistry: Chemoselective Addition of Organolithium and Grignard Reagents to Ketones in Air.
Authors: Vidal Cristian , Garcia‐Alvarez Joaquin , Hernan‐Gomez Alberto , Kennedy Alan R. , Hevia Eva
Published: November 2014

Commercial solutions of metal organyls either in THF, hexanes or Bu2O are used in these reactions.
ChemInform Abstract: PhICl2‐Mediated Conversion of Enamines into α,N‐Dichloroimines and Their Reverse Conversion Mediated by Zinc in Methanol.
Authors: Tang Linlin , Zhang‐Negrerie Daisy , Du Yunfei , Zhao Kang
Published: November 2014

A novel method for the synthesis of α,N‐dichloroimines through chlorination of enamines with PhICl2 as chlorine source is presented.