bluuebunny/crossref_metadata_2025_split huggingface dataset:
Theory and generation of conditional, scalable sub‐Gaussian random fields
Authors: Panzeri M. , Riva M. , Guadagnini A. , Neuman S.P. 
Published: February 2016

AbstractMany earth and environmental (as well as a host of other) variables, Y, and their spatial (or temporal) increments, ΔY, exhibit non‐Gaussian statistical scaling. Previously we were able to capture key aspects of such non‐Gaussian scaling by treating Y and/or ΔY as sub‐Gaussian random fields (or processes). This however left unaddressed the empirical finding that whereas sample frequency distributions of Y tend to display relatively mild non‐Gaussian peaks and tails, those of ΔY often reveal peaks that grow sharper and tails that become heavier with decreasing separation distance or lag. Recently we proposed a generalized sub‐Gaussian model (GSG) which resolves this apparent inconsistency between the statistical scaling behaviors of observed variables and their increments. We presented an algorithm to generate unconditional random realizations of statistically isotropic or anisotropic GSG functions and illustrated it in two dimensions. Most importantly, we demonstrated the feasibility of estimating all parameters of a GSG model underlying a single realization of Y by analyzing jointly spatial moments of Y data and corresponding increments, ΔY. Here, we extend our GSG model to account for noisy measurements of Y at a discrete set of points in space (or time), present an algorithm to generate conditional realizations of corresponding isotropic or anisotropic random fields, introduce two approximate versions of this algorithm to reduce CPU time, and explore them on one and two‐dimensional synthetic test cases.
Throat aurora: The ionospheric signature of magnetosheath particles penetrating into the magnetosphere
Authors: Han D.‐S. , Nishimura Y. , Lyons L. R. , Hu H.‐Q. , Yang H.‐G. 
Published: February 2016

AbstractThroat aurora is suggested to be generated during magnetospheric cold plasma flowing into the magnetopause reconnection site and to be the ionospheric signature of the newly opened flux from reconnection. By examining simultaneous low‐altitude satellites and ground observations, we confirm that the throat auroras are associated with low‐energy electron and ion precipitation of magnetosheath type and thus provide the first evidence that they occur along open magnetic field lines. Additionally, the observations have important possible implications: (1) solar wind particles can penetrate deep into the magnetosphere and may make significant contributions to the low‐energy plasmas often observed in the dayside outer magnetosphere and (2) localized shapes of the magnetopause and the ionospheric open‐closed field line boundary may be substantially changed, during generation of the throat aurora.
Teenage Offenders' Ability to Detect Deception in Their Peers
Authors: Jupe Louise , Akehurst Lucy , Vernham Zarah , Allen James 
Published: February 2016

SummaryThis study investigated the deception detection abilities of teenage offenders and teenage non‐offenders who made veracity judgments about 12 videotaped interviewees and also explored the behavioural characteristics of teenage liars and truth tellers. The findings revealed that teenage offenders were significantly more accurate in their credibility judgments than teenage non‐offenders. However, the offenders' impressive accuracy rates were not as a consequence of using valid cues to deceit. The feedback hypothesis helps to explain why the offenders were more accurate in their decisions: Operating within a criminal environment may mean that teenage offenders frequently lie and are lied to. Consequently, they receive more feedback than non‐offenders regarding the effectiveness of their lies as well as how successful they are at detecting lies. As a result, their lie detection ability improves. The current study suggests moving away from individual deceptive cues as predictors of deceit towards a more intuitive and holistic approach to lie detection, such as the Brunswikian Lens Model.Copyright © 2016 John Wiley & Sons, Ltd.
Chiral Imidodiphosphoric Acids‐Catalyzed Friedel–Crafts Reactions of Indoles/Pyrroles with 3‐Hydroxy‐indolyloxindoles: Enantioselective Synthesis of 3,3‐Diaryloxindoles
Authors: Zhuo Ming‐Hua , Liu Guo‐Feng , Song Shan‐Liang , An Dong , Gao Jigang , Zheng Liangyu , Zhang Suoqin 
Published: February 2016

AbstractThe first enantioselective Friedel–Crafts alkylation of indoles and pyrroles with 3‐hydroxy‐3‐indolyloxindoles to access two novel types of 3,3‐diaryloxindoles catalyzed by chiral imidodiphosphoric acids has been reported. A range of quaternary carbon centered 3,3‐diaryloxindoles were synthesized in high yield (up to >99%) with excellent enantioselectivity (up to 98% ee) at low catalyst loadings (as low as 0.5 mol%). The Friedel–Crafts reaction between indoles and 3‐hydroxy‐3‐indolyloxindoles is amenable to gram scale syntheses.magnified image
Borrowing Hydrogen Methodology for N‐Benzylation using a π‐Benzylpalladium System in Water
Authors: Hikawa Hidemasa , Koike Toshitaka , Izumi Kyoko , Kikkawa Shoko , Azumaya Isao 
Published: February 2016

AbstractWe demonstrate a borrowing hydrogen methodology using the unique reactivity of the π‐benzylpalladium system in water, which offers an efficient and environmentally friendly N‐monobenzylation of electron‐deficient anilines or 2‐aminopyridine with non‐activated benzylic alcohols under neutral conditions. The crossover experiment using benzyl‐α,α‐d2 alcohol and 3‐methylbenzyl alcohol afforded H/D scrambling products, suggesting that the borrowing hydrogen pathway occurred in our catalytic system. Our simple protocol can accomplish a gram scale reaction of 2‐aminobenzonitrile (76 % isolated yield), and is performed with the use of only 1 mol % Pd(OAc)2 and 2 mol % TPPMS without other additives in water.magnified image
Guanidine Synthesis: Use of Amidines as Guanylating Agents
Authors: Baeten Mattijs , Maes Bert U. W. 
Published: February 2016

AbstractThe use of amidines for the tandem or one‐pot synthesis of guanidines is reported. Guanidines are obtained by oxidative rearrangement of readily available and stable amidines into carbodiimides, followed by in situ reaction with amines. The protocol can be executed under mild reaction conditions (30 °C), in a green solvent (dimethyl carbonate). The amine scope is broad, including sterically hindered, oxidation‐sensitive and chiral amines. Examples for the synthesis of both acyclic and cyclic guanidines are provided. 2‐Propoxyphenyl iodide (2‐PrOPhI) by‐product, generated from the oxidant [N‐(p‐toluenesulfonyl)imino](2‐propoxyphenyl)iodinane (2‐PrOPhINTs), can be isolated in high yields making regeneration of the hypervalent iodine reagent possible. The utility and greenness of the synthetic method versus the state‐of‐the‐art is demonstrated by a new route towards the antihypertensive drug Pinacidil. The process mass intensity (PMI) of the new route is only 24% of the classical one.magnified image
Room‐temperature luminescence decay of colloidal semiconductor quantum dots: Nonexponentiality revisited
Authors: Bodunov Evgeny N. , Danilov Vladimir V. , Panfutova Anastasia S. , Simões Gamboa A. L. 
Published: February 2016

While time‐resolved luminescence spectroscopy is commonly used as a quantitative tool for the analysis of the dynamics of photoexcitation in colloidal semiconductor quantum dots, the interpretation of the virtually ubiquitous nonexponential decay profiles is frequently ambiguous, because the assumption of multiple discrete exponential components with distinct lifetimes for resolving the decays is often arbitrary. Here, an interpretation of the room‐temperature luminescence decay of CdSe/ZnS semiconductor quantum dots in colloidal solutions is presented based on the Kohlrausch relaxation function. It is proposed that the decay can be understood by using the concept of Förster resonance energy transfer (FRET) assuming that the role of acceptors of photoexcitation energy is played by high‐frequency anharmonic molecular vibrations in the environment of the quantum dots. The term EVFRET (Electronic ‐ Vibrational Förster Resonance Energy Transfer) is introduced in order to unequivocally refer to this energy transfer process.
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Design und Synthese von Kohlenstoffnanoröhrensegmenten
Authors: Segawa Yasutomo , Yagi Akiko , Matsui Katsuma , Itami Kenichiro 
Published: February 2016

AbstractEin langfristiges Ziel der organischen Synthesechemie und der Nanokohlenstoffchemie ist die selektive und vorhersagbare Synthese von strukturell gleichförmigen Kohlenstoffnanoröhren (CNTs). Dieser Aufsatz konzentriert sich auf synthetische Arbeiten, die dieses Ziel einer gesteuerten Synthese von chiralen CNTs durch die organische Synthese von CNT‐Segmenten und mithilfe eines durch organische Template vermittelten CNT‐Wachstums in Reichweite bringen.
Facile Preparation of Ni2P with a Sulfur‐Containing Surface Layer by Low‐Temperature Reduction of Ni2P2S6
Authors: Tian Song , Li Xiang , Wang Anjie , Prins Roel , Chen Yongying , Hu Yongkang 
Published: February 2016

AbstractPreparation of Ni2P by temperature‐programmed reduction (TPR) of a phosphate precursor is challenging because the P−O bond is strong. An alternative approach to synthesizing Ni2P, by reduction of nickel hexathiodiphosphate (Ni2P2S6), is presented. Conversion of Ni2P2S6 into Ni2P occurs at 200–220 °C, a temperature much lower than that required by the conventional TPR method (typically 500 °C). A sulfur‐containing layer with a thickness of about 4.7 nm, composed of tiny crystallites, was observed at the surface of the obtained Ni2P catalyst (Ni2P−S). This is a direct observation of the sulfur‐containing layer of Ni2P, or the so‐called nickel phosphosulfide phase. Both the hydrodesulfurization activity and the selective hydrogenation performance of Ni2P‐S were superior to that of the catalyst prepared by the TPR method, suggesting a positive role of sulfur on the surface of Ni2P‐S. These features render Ni2P‐S a legitimate alternative non‐precious metal catalyst for hydrogenation reactions.
Proton Transport in a Highly Conductive Porous Zirconium‐Based Metal–Organic Framework: Molecular Insight
Authors: Borges Daiane Damasceno , Devautour‐Vinot Sabine , Jobic Hervé , Ollivier Jacques , Nouar Farid , Semino Rocio , Devic Thomas , Serre Christian , Paesani Francesco , Maurin Guillaume 
Published: February 2016

AbstractThe water stable UiO‐66(Zr)‐(CO2H)2 MOF exhibits a superprotonic conductivity of 2.3×10−3 S cm−1 at 90 °C and 95 % relative humidity. Quasi‐elastic neutron scattering measurements combined with aMS‐EVB3 molecular dynamics simulations were able to probe individually the dynamics of both confined protons and water molecules and to further reveal that the proton transport is assisted by the formation of a hydrogen‐bonded water network that spans from the tetrahedral to the octahedral cages of this MOF. This is the first joint experimental/modeling study that unambiguously elucidates the proton‐conduction mechanism at the molecular level in a highly conductive MOF.
Iron‐catalyzed Cross‐Coupling of Propargyl Carboxylates and Grignard Reagents: Synthesis of Substituted Allenes
Authors: Kessler Simon N. , Bäckvall Jan‐E. 
Published: February 2016

AbstractPresented herein is a mild, facile, and efficient iron‐catalyzed synthesis of substituted allenes from propargyl carboxylates and Grignard reagents. Only 1–5 mol % of the inexpensive and environmentally benign [Fe(acac)3] at −20 °C was sufficient to afford a broad range of substituted allenes in excellent yields. The method tolerates a variety of functional groups.
Formation of Hybrid Perovskite Tin Iodide Single Crystals by Top‐Seeded Solution Growth
Authors: Dang Yangyang , Zhou Yian , Liu Xiaolong , Ju Dianxing , Xia Shengqing , Xia Haibing , Tao Xutang 
Published: February 2016

AbstractHybrid perovskites have generated a great deal of interest because of their potential in photovoltaic applications. However, the toxicity of lead means that there is interest in finding a nontoxic substitute. Bulk single crystals of both cubic CH3NH3SnI3 and CH(NH2)2SnI3 were obtained by using the top‐seeded solution growth method under an ambient atmosphere. Structural refinement, band gap, thermal properties, and XPS measurements of CH3NH3SnI3 and CH(NH2)2SnI3 single crystals are also reported in detail. These results should pave the way for further applications of CH3NH3SnI3 and CH(NH2)2SnI3.
Organocatalytic, Asymmetric Total Synthesis of (−)‐Haliclonin A
Authors: Guo Lian‐Dong , Huang Xiong‐Zhi , Luo Shi‐Peng , Cao Wen‐Sen , Ruan Yuan‐Ping , Ye Jian‐Liang , Huang Pei‐Qiang 
Published: February 2016

AbstractThe first total synthesis of the alkaloid (−)‐haliclonin A is reported. The asymmetric synthesis relied on a novel organocatalytic asymmetric conjugate addition of nitromethane with 3‐alkenyl cyclohex‐2‐enone to set the stereochemistry of the all‐carbon quaternary stereogenic center. The synthesis also features a Pd‐promoted cyclization to form the 3‐azabicyclo[3,3,1]nonane core, a SmI2‐mediated intermolecular reductive coupling of enone with aldehyde to form the requisite secondary chiral alcohol, ring‐closing alkene and alkyne metathesis reactions to build the two aza‐macrocyclic ring systems, and an unprecedented direct transformation of enol into enone.
Enhanced Electron Transfer Reactivity of a Nonheme Iron(IV)–Imido Complex as Compared to the Iron(IV)‐Oxo Analogue
Authors: Vardhaman Anil Kumar , Lee Yong‐Min , Jung Jieun , Ohkubo Kei , Nam Wonwoo , Fukuzumi Shunichi 
Published: February 2016

AbstractReactions of N,N‐dimethylaniline (DMA) with nonheme iron(IV)‐oxo and iron(IV)‐tosylimido complexes occur via different mechanisms, such as an N‐demethylation of DMA by a nonheme iron(IV)‐oxo complex or an electron transfer dimerization of DMA by a nonheme iron(IV)‐tosylimido complex. The change in the reaction mechanism results from the greatly enhanced electron transfer reactivity of the iron(IV)‐tosylimido complex, such as the much more positive one‐electron reduction potential and the smaller reorganization energy during electron transfer, as compared to the electron transfer properties of the corresponding iron(IV)‐oxo complex.
Characterization of the Oxygen Binding Motif in a Ruthenium Water Oxidation Catalyst by Vibrational Spectroscopy
Authors: Duffy Erin M. , Marsh Brett M. , Voss Jonathan M. , Garand Etienne 
Published: February 2016

AbstractFor homogeneous mononuclear ruthenium water oxidation catalysts, the Ru–O2 complex plays a crucial role in the rate determining step of the catalytic cycle, but the exact nature of this complex is unclear. Herein, the infrared spectra of the [Ru(tpy)(bpy)(O2)]2+ complex (tpy=2,2′:6′,2′′‐terpyridine; bpy=2,2′‐bipyridine) are presented. The complex [Ru(tpy)(bpy)(O2)]2+, formed by gas‐phase reaction of [Ru(tpy)(bpy)]2+ with molecular O2, was isolated by using mass spectrometry and was directly probed by cryogenic ion IR predissociation spectroscopy. Well‐resolved spectral features enable a clear identification of the O−O stretch using 18O2 substitution. The band frequency and intensity indicate that the O2 moiety binds to the Ru center in a side‐on, bidentate manner. Comparisons with DFT calculations highlight the shortcomings of the B3LYP functional in properly depicting the Ru–O2 interaction.
Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low‐Spin Fe(III) Complex
Authors: Ridier Karl , Mondal Abhishake , Boilleau Corentin , Cador Olivier , Gillon Béatrice , Chaboussant Grégory , Le Guennic Boris , Costuas Karine , Lescouëzec Rodrigue 
Published: February 2016

AbstractWe have determined by polarized neutron diffraction (PND) the low‐temperature molecular magnetic susceptibility tensor of the anisotropic low‐spin complex PPh4[FeIII(Tp)(CN)3]⋅H2O. We found the existence of a pronounced molecular easy magnetization axis, almost parallel to the C3 pseudo‐axis of the molecule, which also corresponds to a trigonal elongation direction of the octahedral coordination sphere of the FeIII ion. The PND results are coherent with electron paramagnetic resonance (EPR) spectroscopy, magnetometry, and ab initio investigations. Through this particular example, we demonstrate the capabilities of PND to provide a unique, direct, and straightforward picture of the magnetic anisotropy and susceptibility tensors, offering a clear‐cut way to establish magneto‐structural correlations in paramagnetic molecular complexes.
Bioisosteric Exchange of C‐Chloro and Methyl Substituents: Synthesis and Initial Biological Studies of Atpenin A5 Analogues
Authors: Krautwald Simon , Nilewski Christian , Mori Mihoko , Shiomi Kazuro , Ōmura Satoshi , Carreira Erick M. 
Published: February 2016

AbstractAsymmetric synthesis and initial biological studies of two analogues of a naturally occurring chlorinated antifungal agent, atpenin A5, are described. These analogues were selected on the basis of Cl→CH3 or H3C→Cl exchanges in the side‐chain of atpenin A5. The interchange of chloro and methyl substituents led to complex II inhibitors with equal IC50 values. This suggests that Cl↔Me bioisosteric exchange can be realized in aliphatic settings.
New heteroleptic palladium(II) dithiocarbamates: synthesis, characterization, packing and anticancer activity against five different cancer cell lines
Authors: Khan Shahan Zeb , Amir Muhammad Kashif , Ullah Imdad , Aamir Asma , Pezzuto John M. , Kondratyuk Tamara , Bélanger‐Gariepy Francine , Ali Akbar , Khan Sajid , Zia‐ur‐Rehman  
Published: February 2016

Two new heteroleptic palladium(II) complexes have been synthesized by reacting equimolar quantities of palladium(II) chloride, sodium 4‐(2‐methoxyphenyl)piperazine‐1‐carbodithioate and diphenyl‐p‐tolylphosphine (1) or tri‐p‐tolylphosphine (2). Complexes 1 and 2 have been characterized using elemental analysis, Fourier transform infrared spectroscopy, multinuclear NMR (1H, 13C and 31P) spectroscopy and single‐crystal X‐ray analysis. The latter technique confirms a pseudo square‐planar geometry in which two adjacent positions are occupied by bidentate dithiocarbamate while chloro and substituted triphenylphosphine are present at the remaining two positions. The anticancer activity of both complexes against five different cancer cell lines (LU – human lung carcinoma, established at UIC, Department of Surgical Oncology; MCF7 – human breast adenocarcinoma, ATCC number HTB‐22™; MDA‐MB‐231 – human breast adenocarcinoma, ATCC number HTB‐26™; Hepa‐1c1c7 – mouse liver hepatoma, ATCC number CRL‐2026™; PC‐3 – human prostate adenocarcinoma, ATCC number CRL‐1435™) was determined by MTT assay, revealing 2 has higher activity than 1. A drug–calf thymus DNA binding study with UV–visible spectroscopy reveals a higher DNA binding affinity of 2 (3.511 × 104 M−1) than 1 (4.213 × 103 M−1). Density functional theory studies confirm the relatively more stable nature of 2 than 1. Copyright © 2016 John Wiley & Sons, Ltd.
A reductionist metastasis‐on‐a‐chip platform for in vitro tumor progression modeling and drug screening
Authors: Skardal Aleksander , Devarasetty Mahesh , Forsythe Steven , Atala Anthony , Soker Shay 
Published: February 2016

ABSTRACTCurrent animal and 2‐D cell culture models employed in metastasis research and drug discovery remain poor mimics of human cancer physiology. Here we describe a “metastasis‐on‐a‐chip” system allowing real time tracking of fluorescent colon cancer cells migrating from hydrogel‐fabricated gut constructs to downstream liver constructs within a circulatory fluidic device system that responds to environmental manipulation and drug treatment. Devices consist of two chambers in which gut and liver constructs are housed independently, but are connected in series via circulating fluid flow. Constructs were biofabricated with a hyaluronic acid‐based hydrogel system, capable of a variety of customizations, inside of which representative host tissue cells were suspended and metastatic colon carcinoma tumor foci were created. The host tissue of the constructs expressed normal epithelial markers, which the tumor foci failed to express. Instead, tumor regions lost membrane‐bound adhesion markers, and expressed mesenchymal and proliferative markers, suggesting a metastatic phenotype. Metastatic tumor foci grew in size, eventually disseminating from the intestine construct and entering circulation, subsequently reaching in the liver construct, thus mimicking some of the migratory events observed during metastasis. Lastly, we demonstrated the ability to manipulate the system, including chemically modulating the hydrogel system mechanical properties and administering chemotherapeutic agents, and evaluated the effects of these parameters on invasive tumor migration. These results describe the capability of this early stage metastasis‐on‐a‐chip system to model several important characteristics of human metastasis, thereby demonstrating the potential of the platform for making meaningful advances in cancer investigation and drug discovery. Biotechnol. Bioeng. 2016;113: 2020–2032. © 2016 Wiley Periodicals, Inc.
Designed DNA Surfaces for in Vitro Modulation of Natural Killer Cells
Authors: Garrecht Ruben , Meyer Rebecca , Duppach Janine , Reipschläger Simone , Watzl Carsten , Niemeyer Christof M. 
Published: February 2016

AbstractNatural killer (NK) cells are at the junction of the innate and the adaptive immune response and play a very important role in host defense against viral infections and cancer. They have numerous cell surface receptors that activate or inhibit various intracellular signaling cascades that are then integrated to determine the functional activity of these cells. Here we present a surface‐based approach that aims to tackle the largely unknown molecular mechanisms of signal integration. We use DNA microarrays containing capture oligonucleotides for the DNA‐directed immobilization (DDI) of oligonucleotide‐tagged αCD16 antibodies as ligands for NK cells. We demonstrate that the resulting surfaces can be gradually tuned in terms of ligand density to trigger the activation of living NK cells, as evidenced by degranulation, the release of cytokines, and intracellular Ca2+ flux, measured at the level of single cells.
Adipose stem cells differentiated chondrocytes regenerate damaged cartilage in rat model of osteoarthritis
Authors: Latief Noreen , Raza Fahad Ali , Bhatti Fazal‐Ur‐Rehman , Tarar Moazzam Nazir , Khan Shaheen N. , Riazuddin Sheikh 
Published: February 2016

AbstractTransplantation of mesenchymal stem cells (MSCs) or autologous chondrocytes has been shown to repair damages to articular cartilage due to osteoarthritis (OA). However, survival of transplanted cells is considerably reduced in the osteoarthritic environment and it affects successful outcome of the transplantation of the cells. Differentiated chrondroytes derived from adipose stem cells have been proposed as an alternative source and our study investigated this possibility in rats. We investigated the regenerative potential of ADSCs and DCs in osteoarthritic environment in the repair of cartilage in rats. We found that ADSCs maintained fibroblast morphology in vitro and also expressed CD90 and CD29. Furthermore, ADSCs differentiated into chondrocytes, accompanied by increased level of proteoglycans and expression of chondrocytes specific genes, such as, Acan, and Col2a1. Histological examination of transplanted knee joints showed regeneration of cartilage tissue compared to control OA knee joints. Increase in gene expression for Acan, Col2a1 with concomitant decrease in the expression of Col1a1 suggested formation of hyaline like cartilage. A significant increase in differentiation index was observed in DCs and ADSCs transplanted knee joints (P = 0.0110 vs. P = 0.0429) when compared to that in OA control knee joints. Furthermore, transplanted DCs showed increased proliferation along with reduction in apoptosis as compared to untreated control. In conclusion, DCs showed better survival and regeneration potential as compared with ADSCs in rat model of OA and thus may serve a better option for regeneration of osteoarthritic cartilage.