bluuebunny/crossref_metadata_2025_split huggingface dataset:
Revisiting trends in wetness and dryness in the presence of internal climate variability and water limitations over land
Authors: Kumar Sanjiv , Allan Richard P. , Zwiers Francis , Lawrence David M. , Dirmeyer Paul A. 
Published: December 2015

AbstractA theoretically expected consequence of the intensification of the hydrological cycle under global warming is that on average, wet regions get wetter and dry regions get drier (WWDD). Recent studies, however, have found significant discrepancies between the expected pattern of change and observed changes over land. We assess the WWDD theory in four climate models. We find that the reported discrepancy can be traced to two main issues: (1) unforced internal climate variability strongly affects local wetness and dryness trends and can obscure underlying agreement with WWDD, and (2) dry land regions are not constrained to become drier by enhanced moisture divergence since evaporation cannot exceed precipitation over multiannual time scales. Over land, where the available water does not limit evaporation, a “wet gets wetter” signal predominates. On seasonal time scales, where evaporation can exceed precipitation, trends in wet season becoming wetter and dry season becoming drier are also found.
A new technique for the retrieval of near‐surface vertical current shear from marine X‐band radar images
Authors: Lund B. , Graber H. C. , Tamura H. , Collins C. O. , Varlamov S. M. 
Published: December 2015

AbstractA new method to determine near‐surface vertical current shear from noncoherent marine X‐band radar (MR) data is introduced. A three‐dimensional fast Fourier transform is employed to obtain the wave number‐frequency spectrum of a MR image sequence. Near‐surface currents are estimated from the Doppler‐shifted surface gravity wave signal within the spectrum. They represent a weighted mean of the upper ocean flow. The longer the ocean waves on which the current estimates are based, the greater their effective depth. The novelty lies in the wave number‐dependent retrieval method, yielding ∼100 independent current estimates at effective depths from ∼2 to 8 m per ∼12 min measurement period. First, MR near‐surface vertical current shear measurements are presented using data collected from R/V Roger Revelle during the 2010 Impact of Typhoons on the Ocean in the Pacific experiment in the Philippine Sea. Shipboard acoustic Doppler current profiler (ADCP) and anemometer measurements as well as WAVEWATCH III (WW3) model results are used to demonstrate that results are in accord with physical expectations. The wind and wave‐driven Ekman flow is obtained by subtracting ADCP‐based background currents from the radar measurements. At ∼2 m, it is on average ∼1.6% of the wind speed and ∼38.9° to the right of the wind. With increasing effective depth, the speed factor decreases and the deflection angle increases. Based on WW3 results, the MR‐sensed Stokes drift speed is ∼50% of the Ekman flow at ∼2 m and ∼25% at ∼8 m. These findings are consistent with previous observations and Ekman theory.
Donor‐Acceptor Fluorescent Molecular Rotors Appended with Benzocrown Ethers as Doubly Twisted Intramolecular Charge Transfer Based Ratiometric Acidic pH Sensors
Authors: Umar Shahida , Jha Ajay Kumar , Goel Atul 
Published: December 2015

AbstractA fascinating series of highly fluorescent donor‐acceptor‐appended molecular rotors based on benzocrown ethers has been synthesized. The dimethylamino‐based benzocrown ethers have interesting photophysical properties with good quantum yield and emitted dual fluorescence in polar solvents due to doubly twisted‐intramolecular charge transfer (DT‐ICT) character induced by the dimethylamino group and benzocrown ring. The unique dual fluorescence property of the molecular rotors was explored to develop a ratiometric acidic pH sensor.
Reduced Graphene Oxide–Ag3PO4 Heterostructure: A Direct Z‐Scheme Photocatalyst for Augmented Photoreactivity and Stability
Authors: Samal Alaka , Das D. P. , Nanda K. K. , Mishra B. K. , Das J. , Dash A. 
Published: December 2015

AbstractA visible light driven, direct Z‐scheme reduced graphene oxide–Ag3PO4 (RGO–Ag3PO4) heterostructure was synthesized by means of a simple one‐pot photoreduction route by varying the amount of RGO under visible light illumination. The reduction of graphene oxide (GO) and growth of Ag3PO4 took place simultaneously. The effect of the amount of RGO on the textural properties and photocatalytic activity of the heterostructure was investigated under visible light illumination. Furthermore, total organic carbon (TOC) analysis confirmed 97.1 % mineralization of organic dyes over RGO–Ag3PO4 in just five minutes under visible‐light illumination. The use of different quenchers in the photomineralization suggested the presence of hydroxyl radicals (.OH), superoxide radicals (.O2−), and holes (h+), which play a significant role in the mineralization of organic dyes. In addition to that, clean hydrogen fuel generation was also observed with excellent reusability. The 4 RGO–Ag3PO4 heterostructure has a high H2 evolution rate of 3690 μmol h−1 g−1, which is 6.15 times higher than that of RGO.
Homodiselenacalix[4]arenes: Molecules with Unique Channelled Crystal Structures
Authors: Thomas Joice , Dobrzańska Liliana , Van Meervelt Luc , Quevedo Mario Alfredo , Woźniak Krzysztof , Stachowicz Marcin , Smet Mario , Maes Wouter , Dehaen Wim 
Published: December 2015

AbstractA synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert‐butyl ester groups. Single‐crystal X‐ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy‐substituted macrocycle undergoes a single‐crystal‐to‐single‐crystal transformation during which the molecular structure changes its conformation from 1,3‐alternate (loaded with THF/water) to 1,2‐alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles.
Total Synthesis and Biological Assessment of Mandelalide A
Authors: Brütsch Tobias Michael , Bucher Pascal , Altmann Karl‐Heinz 
Published: December 2015

AbstractA new convergent total synthesis of the marine macrolide mandelalide A (1) has been developed that is based on macrocyclic ring closure by a Shiina‐type macrolactonization and the construction of the requisite precursor seco acid by a highly efficient Sonogashira cross‐coupling reaction between two fragments of comparable complexity. Key steps in the elaboration of the acid building block were the enantioselective, catalytic addition of a protected acetylene to crotonaldehyde and the construction of the tetrahydropyran unit that is embedded in the macrocycle by means of an acid‐catalyzed Prins reaction. The synthesis of the alcohol fragment features the formation of the trisubstituted tetrahydrofuran ring through an acetal cleavage/epoxide opening cascade reaction and a rarely used radical alkynylation of a primary alkyl iodide. Intriguingly, the dihydroxylation of a terminal double bond as part of the synthesis of this building block gave the same major product for both the α‐ and β‐AD‐mix reagents, albeit with moderate or low selectivity. Synthetic mandelalide A (1) was a potent proliferation inhibitor of A549, HT460, and H1299 human lung cancer cells in vitro, but not of SK‐N‐SH neuroblastoma cells. However, in no case did we observe complete cell kill even at the highest compound concentration tested (5 μm).
A Fluorination/Aryl Migration/Cyclization Cascade for the Metal‐Free Synthesis of Fluoro‐Benzoxazepines
Authors: Ulmer Anna , Brunner Christoph , Arnold Andreas M. , Pöthig Alexander , Gulder Tanja 
Published: December 2015

AbstractFluorinated organic molecules are of high interest for many applications across chemical and medical disciplines. Efficient methods for the synthesis of such compounds are thus needed. Within this work, application of the bench‐stable cyclic hypervalent iodine(III) fluoro reagent 1 facilitated the development of an efficient, metal‐free method for the preparation of the novel class of 4‐fluoro‐1,3‐benzoxazepines starting from readily available styrenes. The efficacy and broad applicability of this concept is demonstrated by the synthesis of 20 structurally diverse congeners in high yields, regio‐, and diastereoselectivities. The presented method provides complementary chemoselectivity when compared to the common, commercially available electrophilic fluorination reagents, such as selectfluor. First mechanistic investigations with isotopically labeled substrates reveal a complex reaction mechanism, proceeding via an unusual fluorination/1,2‐aryl migration/cyclization cascade.
B‐cell anergy induces a Th17 shift in a novel B lymphocyte transgenic NOD mouse model, the 116C‐NOD mouse
Authors: Carrascal Jorge , Carrillo Jorge , Arpa Berta , Egia‐Mendikute Leire , Rosell‐Mases Estela , Pujol‐Autonell Irma , Planas Raquel , Mora Conchi , Mauricio Dídac , Ampudia Rosa Maria , Vives‐Pi Marta , Verdaguer Joan 
Published: December 2015

Autoreactive B lymphocytes play a key role as APCs in diaebetogenesis. However, it remains unclear whether B‐cell tolerance is compromised in NOD mice. Here, we describe a new B lymphocyte transgenic NOD mouse model, the 116C‐NOD mouse, where the transgenes derive from an islet‐infiltrating B lymphocyte of a (8.3‐NODxNOR) F1 mouse. The 116C‐NOD mouse produces clonal B lymphocytes with pancreatic islet beta cell specificity. The incidence of T1D in 116C‐NOD mice is decreased in both genders when compared with NOD mice. Moreover, several immune selection mechanisms (including clonal deletion and anergy) acting on the development, phenotype, and function of autoreactive B lymphocytes during T1D development have been identified in the 116C‐NOD mouse. Surprisingly, a more accurate analysis revealed that, despite their anergic phenotype, 116C B cells express some costimulatory molecules after activation, and induce a T‐cell shift toward a Th17 phenotype. Furthermore, this shift on T lymphocytes seems to occur not only when both T and B cells contact, but also when helper T (Th) lineage is established. The 116C‐NOD mouse model could be useful to elucidate the mechanisms involved in the generation of Th‐cell lineages.
Steric and Electronic Manipulation of the Anagostic Interaction in 1‐Tetralone Oxime and Imine Complexes of Rhodium(I)
Authors: Harrison John A. , Nielson Alastair J. , Sajjad M. Arif , Saunders Graham C. , Schwerdtfeger Peter 
Published: December 2015

AbstractStructures and properties for the complexes [RhCl(CO)2(L)] (L = 1‐tetralone oximes and imines) containing anagostic C–H separations were obtained from density functional calculations using the dispersion corrected PBE‐D3 functional. Bench‐top syntheses were carried out for several complexes to obtain NMR spectral comparisons. The calculations show a ligand (N)–OH group positions the anagostic hydrogen (H8) more over the metal and (N)–OCMe3 and (N)–CMe3 groups more out towards the chloro ligand where weak H···Cl bonding is involved. This positioning is a result of varying Rh–N bond lengths and steric factors arising below the coordination plane where methyl‐group H atoms can form additional anagostic approaches to the metal and weak hydrogen bonds with the chloro ligand. QTAIM analysis indicates weak electrostatic repulsion for the Rh···H8 approaches. Disparity between the metal and C–H bond orbital energies precludes covalency. Both σ and π‐withdrawing substituents para to C8 increase the H8 positive charge lengthening the Rh···H8 separation; σ and π‐donating substituents decrease the charge and shorten the separation. For (N)–OH ligands, the C7‐alkyl groups Me, CHMe2 and CMe3 do not affect the lengths of the Rh···H8 separations by a steric effect and no significant electronic effects are observed for C7‐NO2, OMe or F substituents. A combination of an (N)‐CMe3 group and electron‐donating groups at C5 and C7 of the aromatic ring do not effect the Rh···H8 separation but the Rh···C8 separation decreases significantly leading to a C‐anagostic interaction. For all the complexes the ligand adapts to accommodate the anagostic approaches.
Biopsychosocial Correlates of Binge Eating Disorder in Caucasian and African American Women with Obesity in Primary Care Settings
Authors: Udo Tomoko , White Marney A. , Lydecker Janet L. , Barnes Rachel D. , Genao Inginia , Garcia Rina , Masheb Robin M. , Grilo Carlos M. 
Published: December 2015

AbstractThis study examined racial differences in eating‐disorder psychopathology, eating/weight‐related histories, and biopsychosocial correlates in women (n = 53 Caucasian and n = 56 African American) with comorbid binge eating disorder (BED) and obesity seeking treatment in primary care settings. Caucasians reported significantly earlier onset of binge eating, dieting, and overweight, and greater number of times dieting than African American. The rate of metabolic syndrome did not differ by race. Caucasians had significantly elevated triglycerides whereas African Americans showed poorer glycaemic control (higher glycated haemoglobin A1c [HbA1c]), and significantly higher diastolic blood pressure. There were no significant racial differences in features of eating disorders, depressive symptoms, or mental and physical health functioning. The clinical presentation of eating‐disorder psychopathology and associated psychosocial functioning differed little by race among obese women with BED seeking treatment in primary care settings. Clinicians should assess for and institute appropriate interventions for comorbid BED and obesity in both African American and Caucasian patients. Copyright © 2015 John Wiley & Sons, Ltd and Eating Disorders Association.
Chemical and in vitro cytotoxicity evaluation of essential oil from Eucalyptus citriodora fruits growing in the Northwestern Himalaya, India
Authors: Koundal Rajkesh , Kumar Dharmesh , Walia Mayanka , Kumar Ashish , Thakur Soni , Chand Gopi , Padwad Yogendra S. , Agnihotri Vijai K. 
Published: December 2015

AbstractEucalyptus citriodora is a well‐known source of essential oil. Essential oil from the fruit's of E. citriodora was extracted using the hydrodistillation method with the help of a Clevenger‐type apparatus (yield 0.23%). The phytochemicals composition of the oil was evaluated using gas chromatography (GC), GC/ mass spectrometry (MS) and nuclear magnetic resonance (NMR) techniques. The essential oil was found to be a complex mixture of mono‐ and sesquiterpenoids. The major chemical constituents identified were α‐pinene (54.1 g/100 g), γ‐terpinene (8.6 g/100 g), E‐caryophyllene (6.6 g/100 g), β‐pinene (6.3 g/100 g), limonene (5.5 g/100 g) and 1,8‐cineole (4.3 g/100 g). In vitro cytotoxicity of the essential oil was evaluated using the sulphorhodamine B (SRB) assay against human lung carcinoma (A549), human epithelial cervix carcinoma (HeLa) and Chinese hamster ovarian carcinoma (CHOK1) cells. The IC50 values of the E. citriodora fruits essential oil against A549, HeLa and CHOK1 cells ranged from 87.5 to 96.8 µg/ml. The toxicity of the isolated essential oil was also assessed against human lymphocytes using the [3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide] (MTT) assay. Essential oil possesses significant cytotoxic activity. The aim of the present study was to search the Northwestern Himalaya for the new potent source of toxicologically safe essential oils. This is a first report on the chemical composition and cytotoxicity of essential oil extracted from the fruit's of E. citriodora. Copyright © 2015 John Wiley & Sons, Ltd.
Crystal size distribution analysis of plagioclase from gabbro‐anorthosite suite of Kuliana, Orissa, eastern India: implications for textural coarsening in a static magma chamber
Authors: Chakraborti Tushar Mouli , Ray Arijit , Deb Gautam Kumar 
Published: December 2015

AbstractThe layered gabbro‐anorthosite suite in the eastern Indian shield is ideal for a texture based study of the crystallization history of a mafic magma in a static magma chamber. The magmatic suite comprises 40–150 m thick persistent layers of different lithounits, which have been divided into two cycles. The lower cycle (I) is represented from bottom to top by gabbro, gabbronorite, leucogabbronorite, anorthositic gabbronorite and anorthositic gabbro. The upper cycle (II) is similar to cycle I, except that the anorthositic gabbronorite and anorthositic gabbro units are not present there. The characteristic textures of different lithounits in each cycle repeats with repetition in lithology. Distinctive textures observed in the suite have been classified into three categories, Types I, II and III. Adcumulus growth was the principle crystallization mechanism for Types I and III textures, which are characteristically present in the lower layers of cycle I and cycle II. The upper layers of cycle I show Type II texture, typically with bimodal size distribution of plagioclase, and pyroxene oikocrysts. Thus, Type II texture indicates a possible interplay between adcumulus growth and either polybaric crystallization or textural coarsening processes. Electron microprobe analysis (EPMA) data indicate uniform composition of plagioclase (An76–85), both from inclusions in pyroxene oikocrysts and from groundmass grains, hence ruling out the possibility of involvement of the polybaric crystallization in the layers with Type II texture. Crystal size distribution (CSD) analysis of plagioclase grains stands for textural coarsening process, and the graphical plots have been utilized to quantify the process. P‐T calculation using EPMA data from selected pyroxene grains suggests that the textural coarsening took place at about 13.3 kb pressure and 990 °C temperature. We propose that adcumulus growth operating in a static magma chamber for a long period of time might have created conditions conducive for textural coarsening process to take place. Copyright © 2015 John Wiley & Sons, Ltd.
Planetary scale modulations in aerosol properties at Delhi, in the Indo‐Gangetic Plain: a quantitative analysis from intra‐seasonal to inter‐annual timescales
Authors: Beegum S. Naseema , Lodhi Neelesh K. , Singh Sachchidanand 
Published: December 2015

ABSTRACTAnalysis of the long‐term time‐series data on aerosol parameters at Delhi, an urban city in the western part of Indo‐Gangetic Plain (IGP), brought out certain interesting findings. The time‐series data are observed to be a complex function of different periodicities varying from intra‐seasonal to inter‐annual timescales. Detailed investigations of the periodicities in conjunction with the meteorological data demonstrated the prevalence of four periodicities such as intra‐seasonal (periodicities of ∼2–3 months, significant at shorter wavelengths), semi‐annual oscillation (SAO, ∼6 months), annual oscillation (AO, ∼12 months) and quasi‐biennial oscillation (QBO, ∼2 years) and quasi‐triennial oscillation (QTO, ∼3 years) at the measurement site in varying amplitudes. The AO and SAO are the dominant components in the aerosol optical depth (AOD) as well as in the Angstrom parameters with a combined contribution of ∼40% to the climatological mean and are attributed to the changes in the prevailing meteorological conditions, which are conducive for either production, transport and/or size‐transformation processes. Among the inter‐annual variability in aerosol parameters, the most significant mode observed is the QTO and is found to be associated with the ENSO variability in the tropical pacific region. While the intra‐seasonal fluctuations (∼2–3 months) observed in AOD (at shorter wavelengths) are associated with the eastward propagating Madden–Julian oscillations (MJO) in the lower troposphere, the biennial variability is related with variability in the meteorology of the upper and lower atmospheric regions. Periodicity analysis on aerosol parameters is useful to determine its predictability in the atmosphere.
Effect of Supramolecular Interchain Sticking on the Low‐Frequency Relaxation of Transient Polymer Networks
Authors: Seiffert Sebastian 
Published: December 2015

Supramolecular polymer networks and gels often exhibit three effects in rheology as a function of increasing strength and extent of transient chain interlinkage: (i) the longest relaxation time increases, (ii) the elastic part of the complex shear modulus on timescales longer than that increases, and (iii) the frequency‐dependent power‐law scaling of this modulus gets shallower in this regime. In a recent report, these effects have been systematically assessed by comparing transient polymer networks derived from a common precursor modified with different extents of a common hydrogen‐bonding supramolecular sticker. In this communication, complementary studies are discussed that are based on a set of polymers also derived from a common precursor but all modified with the same extent (4.8%) of very different supramolecular crosslinking motifs. This comparison reveals that effect (iii) can be rationalized by exacerbation of polydispersity effects to the relaxation time spectrum if supramolecular interchain sticking is present. In addition, effect (ii) is addressable to a simple thermodynamic argument that appraises the supramolecular sticking contribution to the elastic part of the shear modulus in the relaxation regime.
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Urinary metabolites from mango (Mangifera indica L. cv. Keitt) galloyl derivatives and in vitro hydrolysis of gallotannins in physiological conditions
Authors: Barnes Ryan C. , Krenek Kimberly A. , Meibohm Bernd , Mertens‐Talcott Susanne U. , Talcott Stephen T. 
Published: December 2015

ScopeThe absorption, metabolism, and excretion of mango galloyl derivatives (GD) has not yet been investigated in humans, and studies investigating repeated dosages of polyphenols are limited.Methods and resultsIn this human pilot trial, healthy volunteers (age = 21–38 y, n = 11) consumed 400 g/day of mango‐pulp (cv. Keitt) for 10 days, and seven metabolites of gallic acid (GA) were characterized and quantified in urine excreted over a 12 h period. Pyrogallol‐O‐sulfate and deoxypyrogallol‐O‐sulfate were found to be significantly more excreted between days 1 and 10 (p < 0.05) from 28.5 to 55.4 mg and 23.6 to 47.7 mg, respectively. Additionally, the in vitro hydrolysis of gallotannins (GTs) was monitored at physiological pH and temperature conditions, and after 4 h a significant (p < 0.05) shift in composition from relativity high to low molecular weight GTs was observed.ConclusionSeven metabolites of GA were identified in the urine of healthy volunteers, and two microbial metabolites were found to be significantly more excreted following 10 days of mango consumption. Mango GTs were also found to release free GA in conditions similar to the intestines. GTs may serve as a pool of pro‐GA compounds that can be absorbed or undergo microbial metabolism.