bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phylogenomics in Cactaceae: A case study using the chollas sensu lato (Cylindropuntieae, Opuntioideae) reveals a common pattern out of the Chihuahuan and Sonoran deserts
Authors: Majure Lucas C. , Baker Marc A. , Cloud‐Hughes Michelle , Salywon Andrew , Neubig Kurt M. 
Published: September 2019

PremiseAlthough numerous phylogenetic studies have been conducted in Cactaceae, whole‐plastome datasets have not been employed. We used the chollas to develop a plastome dataset for phylogeny reconstruction to test species relationships, biogeography, clade age, and morphological evolution.MethodsWe developed a plastome dataset for most known diploid members of the chollas (42 taxa) as well as for other members of Cylindropuntieae. Paired‐end, raw reads from genome skimming were reference‐mapped onto a de novo plastome assembly of one species of cholla, Cylindropuntia bigelovii, and were used to build our plastome dataset, which was analyzed using various methods.ResultsOur plastome dataset resolved the phylogeny of the chollas, including most interspecific and intraspecific relationships. Tribe Cylindropuntieae arose ~18 mya, during the early Miocene in southern South America, and is supported as sister to the South American clade Tephrocacteae. The (Micropuntia (Cylindropuntia + Grusonia)) clade most likely originated in the Chihuahuan Desert region around 16 mya and then migrated into other North American desert regions. Key morphological characters for recognizing traditional taxonomic series in Cylindropuntia (e.g., spiny fruit) are mostly homoplasious.ConclusionsThis study provides the first comprehensive plastome phylogeny for any clade within Cactaceae. Although the chollas s.l. are widespread throughout western North American deserts, their most recent common ancestor likely arose in the Chihuahuan Desert region during the mid‐Miocene, with much of their species diversity arising in the early to mid‐Pliocene, a pattern strikingly similar to those found in other western North American desert groups.
Manganese‐Catalyzed Oxime‐Directed ortho‐C−H Amidation in Ionic Liquids
Authors: Kong Xianqiang , Xu Bo 
Published: September 2019

AbstractWe have developed an efficient amidation of aromatic oximes via C−H bond activation using readily available sulfonyl azides as amidation reagents. This reaction is catalyzed by a base metal catalyst system – MnBr(CO)5/[Hmim]OTf. Our method offers excellent chemical yields and regioselectivity with good functional group tolerance. The reusability of MnBr(CO)5/[Hmim]OTf system makes it relatively practical for large scale C−H amidations.
Synthesis of α‐Substituted Succinimides from Glyoxal and Ketene N,S‐Acetals
Authors: Xu Qi , Zheng Baihui , Pan Ling , Liu Qun , Li Yifei 
Published: September 2019

AbstractThe reaction of ketene N,S‐acetals with glyoxal for the efficient synthesis of α‐ketosuccinimides is described. Promoted by concentrated hydrobromide, the reaction proceeded under mild aqueous, metal‐free conditions, with broad substrate tolerance. As a result, one C−C, one C−N, and one C−O bond were formed. Mechanistic studies show that this tandem process involves enamine addition, hydrolysis and intramolecular nucleophilic addition. In the proposed mechanism, the amine released as a byproduct plays a promoter role to accelerate the construction of α‐ketosuccinimides.
Intramolecular Arylative Ring Opening of Donor‐Acceptor Cyclopropanes in the Presence of Triflic Acid: Synthesis of 9H‐Fluorenes and 9,10‐Dihydrophenanthrenes
Authors: Wang Dongyang , Zhao Jing , Chen Jun , Xu Qing , Li Huan 
Published: September 2019

AbstractA unique intramolecular arylative ring opening of 2‐biaryl substituted donor‐acceptor cyclopropanes in the presence of triflic acid was found, furnishing 9H‐fluorenes and 9,10‐dihydrophenanthrenes. Chemoselectivity between both products is achieved by modification of the solvent, temperature, and amount of triflic acid. Representative large‐scale experiments were also carried out successfully with good outcomes.
Infiltration pattern of gammadelta T cells and its association with local inflammatory response in the nasal mucosa of patients with allergic rhinitis
Authors: Yang Qintai , Li Chunwei , Wang Weihao , Zheng Rui , Huang Xuekun , Deng Huiyi , Jin Peng , Tan Kaisen , Yan Yan , Wang Deyun 
Published: September 2019

Backgroundgammadelta (γδ) T cells play important roles in allergic lower airway inflammation. However, little is known about their infiltration pattern in the nasal mucosa during upper airway inflammation. This study investigated γδ T cell distribution in nasal tissues of allergic rhinitis (AR) patients and the relationship between γδ T cells and other inflammatory cell types.MethodsA total of 30 patients with septal deviation were examined, including 22 with and 8 without AR. The localization of γδ T cells and other cells (eosinophils, neutrophils, mast cells, macrophages, B cells, cluster of differentiation [CD]4+ T cells, CD8+ T cells, regulatory T cells [Tregs], interferon [IFN]‐γ+ cells, interleukin [IL]17+ cells, and IL10+ cells) was evaluated by histological analysis and immunohistochemistry. T helper cell (Th)1/Th2/Th17 and Treg gene expression was analyzed by quantitative polymerase chain reaction (PCR).Resultsγδ T cells were localized in the epithelium or subepithelial region of nasal mucosa, and their infiltration was higher in AR patients relative to control subjects. The number of γδ T cells was associated with the presence of eosinophils, macrophages, mast cells, B cells, CD8+ T cells, Forkhead box (Fox)p3+ Tregs, IL17+ cells, and IL10+ cells but not of neutrophils or IFN‐γ+ cells. The messenger RNA (mRNA) level of a γδ T cell subunit was positively correlated with those of Th1 genes (T‐bet and IFN‐γ), Th2 cytokine (C‐C motif chemokine ligand 18), and Treg genes (Foxp3 and IL10).Conclusionγδ T cells play multiple roles in mucosal inflammation in AR including immune surveillance and adaptive and innate immune responses.
The Microscopic Structure–Property Relationship of Metal–Organic Polyhedron Nanocomposites
Authors: Zhang Mingxin , Lai Yuyan , Li Mu , Hong Tao , Wang Weiyu , Yu Haitao , Li Lengwan , Zhou Qianjie , Ke Yubin , Zhan Xiaozhi , Zhu Tao , Huang Caili , Yin Panchao 
Published: September 2019

AbstractMonodispersed hairy nanocomposites with typical 2 nm (isophthalic acid)24Cu24 metal–organic polyhedra (MOP) as a core protected by 24 polymer chains with controlled narrow molecular weight distribution has been probed by imaging and scattering studies for the heterogeneity of polymers in the nanocomposites and the confinement effect the MOPs imposing on anchored polymers. Typical confined‐extending surrounded by one entanglement area is proposed to describe the physical states of the polymer chains. This model dictates the counterintuitive thermal and rheological properties and prohibited solvent exchange properties of the nanocomposites, whilst those polymer chain states are tunable and deterministic based on their component inputs. From the relationship between the structure and behavior of the MOP nanocomposites, a MOP‐composited thermoplastic elastomer was obtained, providing practical solutions to improve mechanical/rheological performances and processabilities of inorganic MOPs.
Ion‐Mobility Spectrometry Can Assign Exact Fucosyl Positions in Glycans and Prevent Misinterpretation of Mass‐Spectrometry Data After Gas‐Phase Rearrangement
Authors: Sastre Toraño Javier , Gagarinov Ivan A. , Vos Gaël M. , Broszeit Frederik , Srivastava Apoorva D. , Palmer Martin , Langridge James I. , Aizpurua‐Olaizola Oier , Somovilla Victor J. , Boons Geert‐Jan 
Published: September 2019

AbstractThe fucosylation of glycans leads to diverse structures and is associated with many biological and disease processes. The exact determination of fucoside positions by tandem mass spectrometry (MS/MS) is complicated because rearrangements in the gas phase lead to erroneous structural assignments. Here, we demonstrate that the combined use of ion‐mobility MS and well‐defined synthetic glycan standards can prevent misinterpretation of MS/MS spectra and incorrect structural assignments of fucosylated glycans. We show that fucosyl residues do not migrate to hydroxyl groups but to acetamido moieties of N‐acetylneuraminic acid as well as N‐acetylglucosamine residues and nucleophilic sites of an anomeric tag, yielding specific isomeric fragment ions. This mechanistic insight enables the characterization of unique IMS arrival‐time distributions of the isomers which can be used to accurately determine fucosyl positions in glycans.
Engineering of Ruthenium–Iron Oxide Colloidal Heterostructures: Improved Yields in CO2 Hydrogenation to Hydrocarbons
Authors: Aitbekova Aisulu , Goodman Emmett D. , Wu Liheng , Boubnov Alexey , Hoffman Adam S. , Genc Arda , Cheng Huikai , Casalena Lee , Bare Simon R. , Cargnello Matteo 
Published: September 2019

AbstractCatalytic CO2 reduction to fuels and chemicals is a major pursuit in reducing greenhouse gas emissions. One approach utilizes the reverse water‐gas shift reaction, followed by Fischer–Tropsch synthesis, and iron is a well‐known candidate for this process. Some attempts have been made to modify and improve its reactivity, but resulted in limited success. Now, using ruthenium–iron oxide colloidal heterodimers, close contact between the two phases promotes the reduction of iron oxide via a proximal hydrogen spillover effect, leading to the formation of ruthenium–iron core–shell structures active for the reaction at significantly lower temperatures than in bare iron catalysts. Furthermore, by engineering the iron oxide shell thickness, a fourfold increase in hydrocarbon yield is achieved compared to the heterodimers. This work shows how rational design of colloidal heterostructures can result in materials with significantly improved catalytic performance in CO2 conversion processes.
Electron Transfer in DNA at Electrified Interfaces
Authors: Ferapontova Elena E. 
Published: September 2019

AbstractThe ability of the DNA double helix to transport electrons underlies many life‐centered biological processes and bio‐electronic applications. However, there is little consensus on how efficiently the base pair π‐stacks of DNA mediate electron transport. This minireview scrutinizes the current state‐of‐the‐art knowledge on electron transfer (ET) properties of DNA and its long‐range ability to transfer (mediate) electrical signals at electrified interfaces, without being oxidized or reduced. Complex changes an electric field induces in the DNA structure and its electronic properties govern the efficiency of DNA‐mediated ET at electrodes and allow addressing the existing phenomenological riddles, while recently discovered rectifying properties of DNA contribute both to our understanding of DNA′s ET in living systems and to advances in molecular bioelectronics.
Entrapment of a Pseudo‐Tetrahedral CoII Center by Thioether Sulfur Bound {Co2(μ‐L)} Fragments: Synthesis, Field‐Induced Single‐Ion Magnetism and Catechol Oxidase Mimicking Activity
Authors: Das Manisha , Basak Dipmalya , Trávníček Zdeněk , Vančo Ján , Ray Debashis 
Published: September 2019

AbstractSimultaneous incorporation of both CoII and CoIII ions within a new thioether S‐bearing phenol‐based ligand system, H3L (2,6‐bis‐[{2‐(2‐hydroxyethylthio)ethylimino}methyl]‐4‐methylphenol) formed [Co5] aggregates [CoIICoIII4L2(μ‐OH)2(μ1,3‐O2CCH3)2](ClO4)4⋅H2O (1) and [CoIICoIII4L2(μ‐OH)2(μ1,3‐O2CC2H5)2](ClO4)4⋅H2O (2). The magnetic studies revealed axial zero‐field splitting (ZFS) parameter, D/hc=−23.6 and −24.3 cm−1, and E/D=0.03 and 0.00, respectively for 1 and 2. Dynamic magnetic data confirmed the complexes as SIMs with Ueff/kB=30 K (1) and 33 K (2), and τ0=9.1×10−8 s (1), and 4.3×10−8 s (2). The larger atomic radius of S compared to N gave rise to less variation in the distortion of tetrahedral geometry around central CoII centers, thus affecting the D and Ueff/kB values. Theoretical studies also support the experimental findings and reveal the origin of the anisotropy parameters. In solutions, both 1 and 2 which produce {CoIII2(μ‐L)} units, display solvent‐dependent catechol oxidation behavior toward 3,5‐di‐tert‐butylcatechol in air. The presence of an adjacent CoIII ion tends to assist the electron transfer from the substrate to the metal ion center, enhancing the catalytic oxidation rate.
Ag Nanoparticles Supported on a Resorcinol‐Phenylenediamine‐Based Covalent Organic Framework for Chemical Fixation of CO2
Authors: Chakraborty Debanjan , Shekhar Pragalbh , Singh Himan Dev , Kushwaha Rinku , Vinod C. P. , Vaidhyanathan Ramanathan 
Published: September 2019

AbstractCovalent organic frameworks are a new class of crystalline organic polymers possessing a high surface area and ordered pores. Judicious selection of building blocks leads to strategic heteroatom inclusion into the COF structure. Owing to their high surface area, exceptional stability and molecular tunability, COFs are adopted for various potential applications. The heteroatoms lining in the pores of COF favor synergistic host–guest interaction to enhance a targeted property. In this report, we have synthesized a resorcinol‐phenylenediamine‐based COF which selectively adsorbs CO2 into its micropores (12 Å). The heat of adsorption value (32 kJ mol−1) obtained from the virial model at zero‐loading of CO2 indicates its favorable interaction with the framework. Furthermore, we have anchored small‐sized Ag nanoparticles (≈4–5 nm) on the COF and used the composite for chemical fixation of CO2 to alkylidene cyclic carbonates by reacting with propargyl alcohols under ambient conditions. Ag@COF catalyzes the reaction selectively with an excellent yield of 90 %. Recyclability of the catalyst has been demonstrated up to five consecutive cycles. The post‐catalysis characterizations reveal the integrity of the catalyst even after five reaction cycles. This study emphasizes the ability of COF for simultaneous adsorption and chemical fixation of CO2 into corresponding cyclic carbonates.
Protective effect of glycyrrhizic acid on cerebral ischemia/reperfusion injury via inhibiting HMGB1‐mediated TLR4/NF‐κB pathway
Authors: Yan Sunhong , Fang Chuanqin , Cao Lei , Wang Long , Du Jing , Sun Yue , Tong Xuanxia , Lu Ying , Wu Xiaosan 
Published: September 2019

AbstractCerebral ischemia is caused by various disorders, such as stroke, myocardial infarction, or peripheral vascular disease. The purpose of this paper was to investigate the effects of glycyrrhizic acid (GA) on cerebral ischemia/reperfusion (I/R) injury. Middle cerebral artery occlusion was established to evaluate the effects of GA on cerebral ischemia. In this study, our results showed that GA could dramatically decrease cerebral edema, reduce the neurological deficits, and smaller brain infarct volume was found in the GA treatment group. In serum and brain tissue, GA also increased superoxide dismutase activity. In addition, in serum and brain tissue, GA also dramatically inhibited the secretion of inflammatory cytokines, including interleukin‐1β (IL‐1β), IL‐6, and tumor necrosis factor‐α. Moreover, GA inhibited the expressions of high‐mobility group protein box‐1 (HMGB1)‐mediated TLR4/NF‐κB pathway. Our data determined that GA may provide protective effect on the I/R‐induced cerebral ischemia disease.
Joint mean–covariance random effect model for longitudinal data
Authors: Bai Yongxin , Qian Manling , Tian Maozai 
Published: September 2019

AbstractIn this paper, we consider the inherent association between mean and covariance in the joint mean–covariance modeling and propose a joint mean–covariance random effect model based on the modified Cholesky decomposition for longitudinal data. Meanwhile, we apply M‐H algorithm to simulate the posterior distributions of model parameters. Besides, a computationally efficient Monte Carlo expectation maximization (MCEM) algorithm is developed for carrying out maximum likelihood estimation. Simulation studies show that the model taking into account the inherent association between mean and covariance has smaller standard deviations of the estimators of parameters, which makes the statistical inferences much more reliable. In the real data analysis, the estimation of parameters in the mean and covariance structure is highly efficient.
Microporous scaffolds loaded with immunomodulatory lentivirus to study the contribution of immune cell populations to tumor cell recruitment in vivo
Authors: Bushnell Grace G. , Rao Shreyas S. , Hartfield Rachel M. , Zhang Yining , Oakes Robert S. , Jeruss Jacqueline S. , Shea Lonnie D. 
Published: September 2019

AbstractMetastases are preceded by stochastic formation of a hospitable microenvironment known as the premetastatic niche, which has been difficult to study. Herein, we employ implantable polycaprolactone scaffolds as an engineered premetastatic niche to independently investigate the role of interleukin‐10 (IL10), CXCL12, and CCL2 in recruiting immune and tumor cells and impacting breast cancer cell phenotype via lentiviral overexpression. Lentivirus delivered from scaffolds in vivo achieved sustained transgene expression for 56 days. IL10 lentiviral expression, but not CXCL12 or CCL2, significantly decreased tumor cell recruitment to scaffolds in vivo. Delivery of CXCL12 enhanced CD45+ immune cell recruitment to scaffolds while delivery of IL10 reduced immune cell recruitment. CCL2 did not alter immune cell recruitment. Tumor cell phenotype was investigated using conditioned media from immunomodulated scaffolds, with CXCL12 microenvironments reducing proliferation, and IL10 microenvironments enhancing proliferation. Migration was enhanced with CCL2 and reduced with IL10‐driven microenvironments. Multiple linear regression identified populations of immune cells associated with tumor cell abundance. CD45+ immune and CD8+ T cells were associated with reduced tumor cell abundance, while CD11b+Gr1+ neutrophils and CD4+ T cells were associated with enhanced tumor cell abundance. Collectively, biomaterial scaffolds provide a tool to probe the formation and function of the premetastatic niche.
Volatile fatty acids as novel building blocks for oil‐based chemistry via oleaginous yeast fermentation
Authors: Llamas Mercedes , Magdalena Jose Antonio , González‐Fernández Cristina , Tomás‐Pejó Elia 
Published: September 2019

AbstractMicrobial oils are proposed as a suitable alternative to petroleum‐based chemistry in terms of environmental preservation. These oils have traditionally been studied using sugar‐based feedstock, which implies high costs, substrate limitation, and high contamination risks. In this sense, low‐cost carbon sources such as volatile fatty acids (VFAs) are envisaged as promising building blocks for lipid biosynthesis to produce oil‐based bioproducts. VFAs can be generated from a wide variety of organic wastes through anaerobic digestion and further converted into lipids by oleaginous yeasts (OYs) in a fermentation process. These microorganisms can accumulate in the form of lipid bodies, lipids of up to 60% wt/wt of their biomass. In this context, OY is a promising biotechnological tool for biofuel and bioproduct generation using low‐cost VFA media as substrates. This review covers recent advances in microbial oil production from VFAs. Production of VFAs via anaerobic digestion processes and the involved metabolic pathways are reviewed. The main challenges as well as recent approaches for lipid overproduction are also discussed.
Volatile and Sensory Profiles of Algerian Extra‐Virgin Olive Oil from Souidi and Zeletni Cultivars
Authors: Cherfaoui Maya , Cecchi Teresa , Keciri Sonia , Boudriche Lilya 
Published: September 2019

AbstractIn this study, the volatile and sensory profiles of monovarietal extra‐virgin olive oil (EVOO) from two less widespread Algerian autochthonous cultivars (Souidi and Zeletni) were obtained using headspace solid‐phase microextraction coupled to gas chromatography‐mass spectrometry and a panel test, respectively. A total of 14 and 10 volatile compounds belonging to different chemical classes were identified and quantified in the Souidi and Zeletni EVOOs, respectively. Zeletni EVOO contains 2.07 times more (E)‐2‐hexenal than Souidi EVOO. In addition, the amounts of C6 compounds from LA and LnA, as well as the total amount of the compounds of the LOX pathway were higher in Zeletni than in the Souidi EVOO. Another important finding was the predominance of sesquiterpene β‐ocimene in the composition of the volatile fraction of Souidi EVOO. The sensory profiles of the EVOOs analyzed were characterized by fruity, bitter and pungent sensory positive attributes, perceived at medium intensity in both oils studied.
Synthesis and Relaxometric Characterization of New Poly[N,N‐bis(3‐aminopropyl)glycine] (PAPGly) Dendrons Gd‐Based Contrast Agents and Their in Vivo Study by Using the Dynamic Contrast‐Enhanced MRI Technique at Low Field (1 T)
Authors: Granato Luigi , Longo Dario , Boutry Sébastien , Vander Elst Luce , Henoumont Céline , Aime Silvio , Muller Robert N. , Laurent Sophie 
Published: September 2019

AbstractThe synthesis of poly[N,N‐bis(3‐aminopropyl)glycine] (PAPGly) dendrons Gd‐based contrast agents (GdCAs) via an orthogonal protection of the different functional groups and an activation/coupling strategy wherein a specific number of synthetic steps add a generation to the existing dendron has been described. The aim of this protocol is to build up two different generations of dendrons (G‐0 or dendron's core, and G‐1) with peripheral NH2 groups to conjugate a 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid (DO3A) derivative and afterwards to chelate with Gd3+ paramagnetic ions. These complexes, which have a well‐defined molecular weight, are of relevance to MRI as an attempt to gain higher 1H relaxivity by slowing down the rotation of molecule compared to monomeric Gd(III) complexes used as contrast agents and to increase the number of paramagnetic centers present in one molecular structure. From the study of their water 1H longitudinal relaxation rate at different magnetic fields (NMRD, Nuclear Magnetic Relaxation Dispersion) and by evaluating the variable temperature 17O‐NMR data we determined the parameters characterizing the water exchange rate and the rotational correlation time of each complex, both affecting 1H relaxivity. Furthermore, these two novel PAPGly GdCAs were objects of i) an in vivo study to determine their biodistributions in healthy C57 mice at several time points, and ii) the Dynamic Contrast‐Enhanced MRI (DCE‐MRI) approach to assess their contrast efficiency measured in the tumor region of C57BL/6 mice transplanted subcutaneously with B16‐F10 melanoma cells. The aim of the comparison of these two dendrons GdCAs, having different molecular weights (MW), is to understand how MW and relaxivity may influence the contrast enhancement capabilities in vivo at low magnetic field (1 T). Significant contrast enhancement was observed in several organs (vessel, spleen and liver), already at 5 min post‐injection, for the investigated CAs. Moreover, these CAs induced a marked contrast enhancement in the tumor region, thanks to the enhanced permeability retention effect of those macromolecular structures.