bluuebunny/crossref_metadata_2025 huggingface dataset:
Total Chemical Synthesis of SUMO and SUMO‐Based Probes for Profiling the Activity of SUMO‐Specific Proteases
Authors: Mulder Monique P. C. , Merkx Remco , Witting Katharina F. , Hameed Dharjath S. , El Atmioui Dris , Lelieveld Lindsey , Liebelt Frauke , Neefjes Jacques , Berlin Ilana , Vertegaal Alfred C. O. , Ovaa Huib
Published: May 2018

SUMO is a post‐translational modifier critical for cell cycle progression and genome stability that plays a role in tumorigenesis, thus rendering SUMO‐specific enzymes potential pharmacological targets. However, the systematic generation of tools for the activity profiling of SUMO‐specific enzymes has proven challenging. We developed a diversifiable synthetic platform for SUMO‐based probes by using a direct linear synthesis method, which permits N‐ and C‐terminal labelling to incorporate dyes and reactive warheads, respectively. In this manner, activity‐based probes (ABPs) for SUMO‐1, SUMO‐2, and SUMO‐3‐specific proteases were generated and validated in cells using gel‐based assays and confocal microscopy. We further expanded our toolbox with the synthesis of a K11‐linked diSUMO‐2 probe to study the proteolytic cleavage of SUMO chains. Together, these ABPs demonstrate the versatility and specificity of our synthetic SUMO platform for in vitro and in vivo characterization of the SUMO protease family.
Dianionic Titanyl and Vanadyl (Cation+)2[MIVO(Pc4−)]2− Phthalocyanine Salts Containing Pc4− Macrocycles
Authors: Konarev Dmitri V. , Kuzmin Alexey V. , Khasanov Salavat S. , Litvinov Alexey L. , Otsuka Akihiro , Yamochi Hideki , Kitagawa Hiroshi , Lyubovskaya Rimma N.
Published: May 2018

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4N+)2[MIVO(Pc4−)]2− (M=Ti, V) and (Bu3MeP+)2[MIVO(Pc4−)]2− (M=Ti, V) with [MIVO(Pc4−)]2− dianions were synthesized and characterized. Reduction of MIVO(Pc2−) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4N+ or Bu3MeP+ is exclusive to the phthalocyanine centers, forming Pc4− species. During reduction, the metal +4 charge did not change, implying that Pc is an non‐innocent ligand. The Pc negative charge increase caused the C−N(pyr) bonds to elongate and the C−N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn–Teller effects are significant in the [eg(π*)]2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q‐bands were observed in the UV/Vis/NIR when MIVO(Pc2−) was reduced to [MIVO(Pc.3−)].− and [MIVO(Pc4−)]2−. From magnetic measurements, [TiIVO(Pc4−)]2− was found to be diamagnetic and (Bu4N+)2[VIVO(Pc4−)]2− and (Bu3MeP+)2[VIVO(Pc4−)]2− were found to have magnetic moments of 1.72–1.78 μB corresponding to an S=1/2 spin state owing to VIV electron spin. As a result, two latter salts show EPR signals with VIV hyperfine coupling.
Determination of Asbestos–Cement Pipe Deterioration Rate Using Accelerated Acid Degradation
Authors: Ghirmay Abiy M. , Wood Clinton M.
Published: May 2018

Deterioration of asbestos–cement (AC) water pipes was assessed using accelerated acid exposure experiments coupled with measurements of physical and mechanical properties. The experiments were conducted in three phases using a strong acid (nitric acid) at concentrations ranging from 0.00158 to 3.16 M. The AC pipe deterioration was determined using phenolphthalein staining and the measurement of calcium and magnesium. Results from the experiment indicate that a linear rate of deterioration with time is the most appropriate for estimating the rate of deterioration in the field and for estimating the remaining service life of the AC pipe. In addition, the use of high‐concentration acids to understand the strength loss of AC pipes in the field was evaluated by comparing the crushing and hydrostatic capacity of a full‐scale acid‐degraded specimen and a naturally degraded specimen. Similar loss of crushing and hydrostatic capacity with increasing deterioration was observed between the acid‐degraded and naturally degraded specimen.
Biocatalytic potential of Streptomyces spp. isolates from rhizosphere of plants and mycorrhizosphere of fungi
Authors: Spasic Jelena , Mandic Mina , Radivojevic Jelena , Jeremic Sanja , Vasiljevic Branka , Nikodinovic‐Runic Jasmina , Djokic Lidija
Published: May 2018

Biocatalytic potential of Streptomyces strains isolated from the rhizosphere of plants and from mycorrhizosphere of fungi has been investigated. A total of 118 Streptomyces isolates were selected and functionally screened for 10 different biotechnologically important enzymatic activities: hydrolase (cellulase, cutinase, gelatinase, lipase, protease, polyhydroxyalkanoate (PHA) depolymerase), phenol oxidase and peroxidase (laccase, tyrosinase, and lignin peroxidase), and aminotransferase. Out of 118 tested Streptomyces spp., 90% showed at least one enzymatic activity. The most abundant were enzymes involved in the biomass degradation, as the production of cutinase, cellulase, and lignin peroxidase were detected in 31%, 40%, and 48% of the isolates, respectively. The improved specific activities of lipase (isolates BV315 and BV100) and tyrosinase (isolates BV87 and BV88) were shown in comparison with the industrially relevant activities of Pseudomonas strains. Plant rhizosphere soils were more prolific source of Streptomyces strains with biocatalytic potential in comparison with mycorrhizosphere soils. Overall, 284 enzyme activities among 118 Streptomyces isolates have been detected. This is the first comprehensive screening of Streptomyces isolates from rhizosphere and mycorrhizosphere soils for novel biocatalysts, showing that specific environmental habitats, such as rhizosphere soils, are “treasure troves” of Streptomyces with biocatalytic potential.
Conceptual process design and ­simulation of microalgae oil ­conversion to aviation fuel
Authors: Bwapwa Joseph K. , Anandraj Akash , Trois Cristina
Published: May 2018

Microalgae oil can be converted into aviation fuel to reduce dependence on fossil fuels and decrease the carbon footprint. This could be a significant step toward sustainable energy resources that have the potential to produce ‘drop‐in’ fuels. Algae‐based fuels are potential substitutes for fossil fuels due to the quality of their crude oil. However, this is only possible if appropriate conversion processes are undertaken. Conversely, microalgae species have low lipid content and biomass harvesting is still an energy‐demanding process. In this study, a conceptual design is developed for the conversion of microalgae oil to jet fuel. It is based on a process undertaken in the laboratory using a species named Nannochloropsis sp. Nutrients and CO2 were supplied to the growing culture for effective growth. Biomass harvesting was completed on the tenth day of the growth cycle. It was followed by physiological modification to improve lipid content. Finally, crude oil extraction was followed by bio‐oil hydrocracking at 350 °C, and fractionation of cracked bio‐oil between 70 and 300 °C to separate light‐, middle‐, and heavy‐end hydrocarbons for use in the production of jet fuel. During simulation, reforming and upgrading processes were added to the design to enhance the quality of the jet fuel to be produced on large scale in the future. The study, including the results, suggests that it is technically feasible to convert microalgae oil into jet fuel because of the similarity between algae bio‐oil and petroleum crude oil. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd
MANF attenuates neuronal apoptosis and promotes behavioral recovery via Akt/MDM‐2/p53 pathway after traumatic spinal cord injury in rats
Authors: Gao Liansheng , Xu Weilin , Fan Shuangbo , Li Tao , Zhao Tengfei , Ying Guangyu , Zheng Jingwei , Li Jianru , Zhang Zhongyuan , Yan Feng , Zhu Yongjian , Chen Gao
Published: May 2018

The aim of this study was to investigate the potential effect and mechanism of action of MANF in attenuating neuronal apoptosis following t‐SCI. A clip compressive model was used to induce a crush injury of the spinal cord in a total of 230 rats. The Basso, Beattie, and Bresnahan (BBB) score, spinal cord water content, and blood spinal cord barrier (BSCB) permeability were evaluated. The expression levels of MANF and its downstream proteins were examined by western blotting. Immunofluorescence staining of MANF, NeuN, GFAP, Iba‐1, cleaved caspase‐3, and TUNEL staining were also performed. Cells were counted in six randomly selected fields in the gray matter regions of the sections from two spinal cord sites (2 mm rostral and caudal to the epicenter of the injury) per sample. A cell‐based mechanical injury model was also conducted using SH‐SY5Y cells. Cell apoptosis and viability were assessed by flow cytometry, an MTT assay, and trypan blue staining. Subcellular structures were observed by transmission electron microscopy. MANF was mainly expressed in neurons. The expression levels of MANF, and its downstream target, p‐Akt, were gradually increased and after t‐SCI. Treatment with MANF increased Bcl‐2 and decreased Bax and CC‐3 levels; these effects were reversed on treatment with MK2206. The BBB score, spinal cord water content, and BSCB destruction were also ameliorated by MANF treatment. MANF decreases neuronal apoptosis and improves neurological function through Akt/MDM‐2/p53 pathway after t‐SCI. Therefore, MANF might be a potential treatment for patients with t‐SCI. © 2018 BioFactors, 44(4):369–386, 2018
Prehospital identification of factors associated with death during one‐year follow‐up after acute stroke
Authors: Hansson Per‐Olof , Andersson Hagiwara Magnus , Brink Peter , Herlitz Johan , Wireklint Sundström Birgitta
Published: May 2018

Objectives

In acute stroke, the risk of death and neurological sequelae are obvious threats. The aim of the study was to evaluate the association between various clinical factors identified by the emergency medical service (EMS) system before arriving at hospital and the risk of death during the subsequent year among patients with a confirmed stroke.

Material and Methods

All patients with a diagnosis of stroke as the primary diagnosis admitted to a hospital in western Sweden (1.6 million inhabitants) during a four‐month period were included. There were no exclusion criteria.

Results

In all, 1,028 patients with a confirmed diagnosis of stroke who used the EMS were included in the analyses. Among these patients, 360 (35%) died during the following year. Factors that were independently associated with an increased risk of death were as follows: (1) high age, per year OR 1.07; 95% CI 1.05‐1.09; (2) a history of heart failure, OR 2.08; 95% CI 1.26‐3.42; (3) an oxygen saturation of <90%, OR 8.05; 95% CI 3.33‐22.64; and (4) a decreased level of consciousness, OR 2.19; 95% CI 1.61‐3.03.

Conclusions

Among patients with a stroke, four factors identified before arrival at hospital were associated with a risk of death during the following year. They were reflected in the patients’ age, previous clinical history, respiratory function, and the function of the central nervous system.
Phaneros: Visibility‐based framework for massive peer‐to‐peer virtual environments
Authors: Çevikbaş Şafak Burak , İşler Veysi
Published: May 2018

Contemporary distributed virtual environments are growing out of terabytes of 3D content and hundreds of thousands of users. Server–client architectures have become inadequate for fulfilling the scalability requirements. The peer‐to‐peer architectures provide inherently scalable, cost‐effective distributed solutions for distributed virtual environments. We present a fully distributed peer‐to‐peer framework, Phaneros, which is capable of providing necessary means to realize more efficient and more scalable massive distributed virtual environments. Using the presented visibility‐aware interest management, Phaneros performs better than existing overlays, achieving single‐hop update dissemination while having lower bandwidth requirements. The provided visibility‐aware 3D streaming scheme distributes 3D content more efficiently without creating any significant load on the server. Our test results show significant improvements over existing frameworks.
Phenolic Profile of Artemisia alba Turra
Authors: Trendafilova Antoaneta , Todorova Milka , Genova Victoria , Peter Samuel , Wolfram Evelyn , Danova Kalina , Evstatieva Luba
Published: May 2018

The aim of this study was to evaluate flower and leaf methanol extracts of Artemisia alba Turra for their total phenolic and flavonoid contents, antioxidant capacity and to investigate their phenolic composition. The flower extract was richer in total phenolics and flavonoids and possessed higher antioxidant activity through DPPH and ABTS assays. The UHPLC‐PDA‐MS analysis of the flower and leaf methanol extracts revealed similar phenolic profile and allowed identification of 31 phenolic compounds (flavonoids, coumarins, and phenolic acids) by comparison with the respective reference compounds or tentatively characterized by their chromatographic behavior, UV patterns, and MS fragmentations. The presence of hispidulin, jaceosidin, desmethoxycentaureidin, and dicaffeoyl esters of quinic acid in A. alba is reported herein for the first time. The distribution of flavonoids in A. alba from different origins was discussed from chemotaxonomic point of view.
Modulation of inflammatory and hormonal parameters in response to testosterone therapy: Effects on the ventral prostate of adult rats
Authors: Mendes Leonardo O. , Castilho Anthony C. S. , Pinho Cristiane F. , Gonçalvez Bianca F. , Razza Eduardo M. , Chuffa Luiz Gustavo A. , Anselmo‐Franci Janete A. , Scarano Wellerson R. , Martinez Francisco E.
Published: May 2018

Testosterone is often recommended in the treatment of several aging‐related conditions. However, there are still questions about the consequences of this therapy in terms of hormonal and inflammatory parameters that are crucial for prostate homeostasis. Thus, we investigate if the testosterone therapy (TT) modulates the hormone receptors and inflammatory cytokines in the ventral prostate of adult rats. Wistar rats aging 150 days were divided into two experimental groups (n = 10/group): T: received subcutaneous injections of testosterone cypionate (5 mg/kg body weight) diluted in corn oil every other day for 4 weeks; and C: received corn oil as vehicle. Animals were euthanized at 180 days old by decapitation. Blood was collected to obtain hormone and cytokines concentrations. The ventral prostate was dissected and processed for light microscope and molecular analyses. Relative ventral prostate weight and epithelial compartment were increased after TT. The number of intact and degranulated mast cells was reduced in the T group. Plasma testosterone, DHT and intraprostatic testosterone concentrations were higher in the T group. TT leads to an increase in cell proliferation and up‐regulation of AR, ERβ, PAR‐4, and NRF2. Importantly, plasma concentration and tissue expression of IL‐10 and TNF‐α were higher after TT. In summary, these results indicate that TT can regulate inflammatory response, with impacts in cytokines and mast cell population, and modulates steroids receptors, important parameters for prostatic homeostasis.
Caesium for Perovskite Solar Cells: An Overview
Authors: Bella Federico , Renzi Polyssena , Cavallo Carmen , Gerbaldi Claudio
Published: May 2018

Perovskite solar cells have the potential to revolutionize the world of photovoltaics, and their efficiency close to 23 % on a lab‐scale recently certified this novel technology as the one with the most rapidly raising performance per year in the whole story of solar cells. With the aim of improving stability, reproducibility and spectral properties of the devices, in the last three years the scientific community strongly focused on Cs‐doping for hybrid (typically, organolead) perovskites. In parallel, to further contrast hygroscopicity and reach thermal stability, research has also been carried out to achieve the development of all‐inorganic perovskites based on caesium, the performances of which are rapidly increasing. The potential of caesium is further strengthened when it is used as a modifying agent of charge‐carrier layers in solar cells, but also for the preparation of perovskites with peculiar optoelectronic properties for unconventional applications (e.g., in LEDs, photodetectors, sensors, etc.). This Review offers a 360‐degree overview on how caesium can strongly tune the properties and performance of perovskites and relative perovskite‐based devices.
A Unique LnIII{[3.3.1]GaIII Metallacryptate} Series That Possesses Properties of Slow Magnetic Relaxation and Visible/Near‐Infrared Luminescence
Authors: Lutter Jacob C. , Eliseeva Svetlana V. , Kampf Jeff W. , Petoud Stéphane , Pecoraro Vincent L.
Published: May 2018

A new family of [3.3.1] metallacryptates with the general composition [LnGa6(H2shi)(Hshi)(shi)7(C5H5N)] (Ln‐1; shi3−=salicylhydroximate; Ln = Pr, Nd, Sm–Yb) has been synthesized and characterized. Ln‐1 display both interesting magnetic and luminescent properties. Sm‐1 has sharp emission bands in the visible and the near‐infrared (NIR) regions with quantum yield values (
) of 1.64(9) and 5.5(2).10−2 %, respectively. Tb‐1 exhibits a weak green emission (
=1.89(3).10−1 %) while Pr‐1, Nd‐1, Ho‐1, Er‐1, and Yb‐1 possess emission bands in the NIR range with
=3.7(2).10−3 %,
=1.71(5).10−1 %,
=1.1(2).10−3 %,
=7.1(2).10−3 % and
=0.65(3) %. Nd‐1, Dy‐1, and Yb‐1 display slow magnetization relaxation in an applied field, where only Dy‐1 has been observed to follow an Orbach process (Ueff=12.7 K). The combination of NIR emission with magnetic properties makes Nd‐1 and Yb‐1 attractive candidates as smart materials addressable in two manners.
Synthesis of Azaphosphinines by Directed Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions with Na(OCP)
Authors: Hansmann Max M.
Published: May 2018

Herein, a straightforward synthetic approach towards azaphosphinines is reported. The synthesis of 1,3‐ and 1,4‐aza‐λ3‐phosphinines as well as 1,2,4‐diaza‐λ3‐phosphinines by inverse‐electron‐demand hetero‐Diels–Alder reactions of sodium 2‐phosphaethynolate [NaOCP] with triazines and tetrazines is studied. In the case of 1,2,4‐triazines a hetero‐D.A. reaction was developed, which relies on a new directing‐group approach based on the complexation of sodium to form an ionic Do→Na‐OCP tether. The first X‐ray characterization data for aza‐λ3‐phosphinines as well as the first phosphinine triflates are presented.
Quantifying Biomolecular Binding Constants using Video Paper Analytical Devices
Authors: Miller Benjamin S. , Parolo Claudio , Turbé Valérian , Keane Candice E. , Gray Eleanor R. , McKendry Rachel A.
Published: May 2018

A novel ultra‐low‐cost biochemical analysis platform to quantify protein dissociation binding constants and kinetics using paper microfluidics is reported. This approach marries video imaging with one of humankind's oldest materials: paper, requiring no large, expensive laboratory equipment, complex microfluidics or external power. Temporal measurements of nanoparticle–antibody conjugates binding on paper is found to follow the Langmuir Adsorption Model. This is exploited to measure a series of antibody–antigen dissociation constants on paper, showing excellent agreement with a gold‐standard benchtop interferometer. The concept is demonstrated with a camera and low‐end smartphone, 500‐fold cheaper than the reference method, and can be multiplexed to measure ten reactions in parallel. These findings will help to widen access to quantitative analytical biochemistry, for diverse applications spanning disease diagnostics, drug discovery, and environmental analysis in resource‐limited settings.
Structural Analysis of Small‐Molecule Binding to the BAZ2A and BAZ2B Bromodomains
Authors: Dalle Vedove Andrea , Spiliotopoulos Dimitrios , D'Agostino Vito G. , Marchand Jean‐Rémy , Unzue Andrea , Nevado Cristina , Lolli Graziano , Caflisch Amedeo
Published: May 2018

The bromodomain‐containing protein BAZ2A is a validated target in prostate cancer research, whereas the function of its paralogue BAZ2B is still undefined. The bromodomains of BAZ2A and BAZ2B have a similar binding site for their natural ligand, the acetylated lysine side chain. Here, we present an analysis of the binding modes of eight compounds belonging to three distinct chemical classes. For all compounds, the moiety mimicking the natural ligand engages in essentially identical interactions in the BAZ2A and BAZ2B bromodomains. In contrast, the rest of the molecule is partially solvent‐exposed and adopts different orientations with different interactions in the two bromodomains. Some of these differences could be exploited for designing inhibitors with selectivity within the BAZ2 bromodomain subfamily.
Dichlorophenylacrylonitriles as AhR Ligands That Display Selective Breast Cancer Cytotoxicity in vitro
Authors: Baker Jennifer R. , Gilbert Jayne , Paula Stefan , Zhu Xiao , Sakoff Jennette A. , McCluskey Adam
Published: May 2018

Knoevenagel condensation of 3,4‐dichloro‐ and 2,6‐dichlorophenylacetonitriles gave a library of dichlorophenylacrylonitriles. Our leads (Z)‐2‐(3,4‐dichlorophenyl)‐3‐(1H‐pyrrol‐2‐yl)acrylonitrile (5) and (Z)‐2‐(3,4‐dichlorophenyl)‐3‐(4‐nitrophenyl)acrylonitrile (6) displayed 0.56±0.03 and 0.127±0.04 μm growth inhibition (GI50) and 260‐fold selectivity for the MCF‐7 breast cancer cell line. A 2,6‐dichlorophenyl moiety saw a 10‐fold decrease in potency; additional nitrogen moieties (‐NO2) enhanced activity (Z)‐2‐(2,6‐dichloro‐3‐nitrophenyl)‐3‐(2‐nitrophenyl)acrylonitrile (26) and (Z)‐2‐(2,6‐dichloro‐3‐nitrophenyl)‐3‐(3‐nitrophenyl)acrylonitrile (27), with the corresponding ‐NH2 analogues (Z)‐2‐(3‐amino‐2,6‐dichlorophenyl)‐3‐(2‐aminophenyl)acrylonitrile (29) and (Z)‐2‐(3‐amino‐2,6‐dichlorophenyl)‐3‐(3‐aminophenyl)acrylonitrile (30) being more potent. Despite this, both 29 (2.8±0.03 μm) and 30 (2.8±0.03 μm) were found to be 10‐fold less cytotoxic than 6. A bromine moiety effected a 3‐fold enhancement in solubility with (Z)‐3‐(5‐bromo‐1H‐pyrrol‐2‐yl)‐2‐(3,4‐dichlorophenyl)acrylonitrile 18 relative to 5 at 211 μg mL−1. Modeling‐guided synthesis saw the introduction of 4‐aminophenyl substituents (Z)‐3‐(4‐aminophenyl)‐2‐(3,4‐dichlorophenyl)acrylonitrile (35) and (Z)‐N‐(4‐(2‐cyano‐2‐(3,4‐dichlorophenyl)vinyl)phenyl)acetamide (38), with respective GI50 values of 0.030±0.014 and 0.034±0.01 μm. Other analogues such as 35 and 36 were found to have sub‐micromolar potency against our panel of cancer cell lines (HT29, colon; U87 and SJ‐G2, glioblastoma; A2780, ovarian; H460, lung; A431, skin; Du145, prostate; BE2‐C, neuroblastoma; MIA, pancreas; and SMA, murine glioblastoma), except compound 38 against the U87 cell line. A more extensive evaluation of 38 ((Z)‐N‐(4‐(2‐cyano‐2‐(3,4‐dichlorophenyl)vinyl)phenyl)acetamide) in a panel of drug‐resistant breast carcinoma cell lines showed 10–206 nm potency against MDAMB468, T47D, ZR‐75‐1, SKBR3, and BT474. Molecular Operating Environment docking scores showed a good correlation between predicted binding efficiencies and observed MCF‐7 cytotoxicity. This supports the use of this model in the development of breast‐cancer‐specific drugs.
Cancer Stem Cell Migration in Three‐Dimensional Aligned Collagen Matrices
Authors: Ray Arja , Morford Rachel K. , Provenzano Paolo P.
Published: May 2018

Cell migration is strongly influenced by the organization of the surrounding 3‐D extracellular matrix. In particular, within fibrous solid tumors, carcinoma cell invasion may be directed by patterns of aligned collagen in the extra‐epithelial space. Thus, studying the interactions of heterogeneous populations of cancer cells that include the stem/progenitor‐like cancer stem cell subpopulation and aligned collagen networks is critical to our understanding of carcinoma dissemination. Here, we describe a robust method to generate aligned collagen matrices in vitro that mimic in vivo fiber organization. Subsequently, a protocol is presented for seeding aligned matrices with distinct carcinoma cell subpopulations and performing live cell imaging and quantitative analysis of cell migration. Together, the engineered constructs and the imaging techniques laid out here provide a platform to study cancer stem cell migration in 3‐D anisotropic collagen with real‐time visualization of cellular interactions with the fibrous matrix. © 2018 by John Wiley & Sons, Inc.
W(OTf)6‐Catalyzed Synthesis of γ‐Lactones by Ring Contraction of Macrolides or Ring Closing of Terminal Hydroxyfatty Acids in Ionic Liquid
Authors: Xie Zhong‐Yu , Deng Jin , Fu Yao
Published: May 2018

γ‐Lactones are an important class of fine chemical products and are widely used in perfumes, medicines, pesticides, dyes, and other fields. Herein, a new method for γ‐lactones preparation based on ring contraction was developed. Starting from macrolides, W(OTf)6 was used to catalyze the ring‐opening polymerization then depolymerization. The depolymerization step was not a common ring‐closing process, and the carbon number of the ring was reduced one by one by rearrangement to form the most thermodynamically stable five‐membered ring compounds. γ‐Caprolactone (180 °C for 10 h) was obtained in a yield of 94 % when [EMIM]OTf was used as the solvent, and the yield of isolated product was up to 85 %. The interaction of various components and the reaction mechanism were studied by FTIR spectroscopy and 1H NMR spectroscopy, respectively. Furthermore, γ‐lactones could be produced when the substrate was extended to terminal hydroxyfatty acids. Unexpectedly, the catalyst was poisoned by 1 equivalent of H2O added during the process and thus the yield decreased greatly. The reaction is green and simple, and proceeds in one pot with high atom economy (100 % for macrolides and with water as the only byproduct for terminal hydroxyfatty acid), which provides a promising approach to synthesizing γ‐lactones.
Fluid description of neutral particles in divertor regimes in WEST
Authors: Valentinuzzi M. , Giorgiani G. , Marandet Y. , Bufferand H. , Ciraolo G. , Tamain P. , Serre E. , Ghendrih Ph.
Published: May 2018

A new neutral fluid code has been developed as a necessary step towards a hybrid fluid/kinetic neutral model, to be used in ITER or DEMO simulations, where part of the divertor will be very collisional for neutrals. The neutral fluid code, which is able to handle complex geometries in view of the coupling to Soledge2D, is tested on plasma backgrounds obtained by Soledge2D‐Eirene in WEST geometry, for different divertor regimes, and is found to be in fair agreement with the kinetic Monte Carlo solver Eirene. The differences are due to the simplifications introduced in the fluid model and to the fact that a fluid description is not fully valid in these cases.
Patterns of RSA and observed distress during the still‐face paradigm predict later attachment, compliance and behavior problems: A person‐centered approach
Authors: Qu Jin , Leerkes Esther M.
Published: May 2018

This study examined profiles of infant observed distress and physiological regulation indexed by respiratory sinus arrhythmia (RSA) levels during the still‐face paradigm at 6 months using a person‐centered approach. Mothers and infants (N = 206) participated in the study when infants were 6 months, 1 year, and 2 years old. Attachment was assessed at 1 year via the Strange Situation. Children's compliance behaviors were assessed at 2 years during a toy clean‐up task. Mothers reported children's behavior problems at 4.5 years. Latent profile analysis yielded four profiles: highly distressed, but regulating; over‐regulated; resilient to distress; and under‐regulated. Infants in the “resilient to distress” profile characterized by high RSA levels and low negative affect exhibited the most adaptive outcomes such as lower attachment avoidance, higher compliance, and lower behavior problems. Therefore, this study highlights the importance of considering patterns of behavioral and physiological indicators of infant emotionality together for understanding adaptive functioning.
Integral bHLH factor regulation of cell cycle exit and RGC differentiation
Authors: Maurer Kate A. , Kowalchuk Angelica , Shoja‐Taheri Farnaz , Brown Nadean L.
Published: May 2018

Background: In the developing mouse embryo, the bHLH transcription factor Neurog2 is transiently expressed by retinal progenitor cells and required for the initial wave of neurogenesis. Remarkably, another bHLH factor, Ascl1, normally not present in the embryonic Neurog2 retinal lineage, can rescue the temporal phenotypes of Neurog2 mutants. Results: Here we show that Neurog2 simultaneously promotes terminal cell cycle exit and retinal ganglion cell differentiation, using mitotic window labeling and integrating these results with retinal marker quantifications. We also analyzed the transcriptomes of E12.5 GFP‐expressing cells from Neurog2GFP/+, Neurog2GFP/GFP, and Neurog2Ascl1KI/GFP eyes, and validated the most significantly affected genes using qPCR assays. Conclusions: Our data support the hypothesis that Neurog2 acts at the top of a retinal bHLH transcription factor hierarchy. The combined expression levels of these downstream factors are sufficiently induced by ectopic Ascl1 to restore RGC genesis, highlighting the robustness of this gene network during retinal ganglion cell neurogenesis. Developmental Dynamics 247:965‐975, 2018. © 2018 Wiley Periodicals, Inc.
Spring migration patterns, habitat use, and stopover site protection status for two declining waterfowl species wintering in China as revealed by satellite tracking
Authors: Si Yali , Xu Yanjie , Xu Fei , Li Xueyan , Zhang Wenyuan , Wielstra Ben , Wei Jie , Liu Guanhua , Luo Hao , Takekawa John , Balachandran Sivananintha , Zhang Tao , de Boer Willem F. , Prins Herbert H. T. , Gong Peng
Published: May 2018

East Asian migratory waterfowl have greatly declined since the 1950s, especially the populations that winter in China. Conservation is severely hampered by the lack of primary information about migration patterns and stopover sites. This study utilizes satellite tracking techniques and advanced spatial analyses to investigate spring migration of the greater white‐fronted goose (Anser albifrons) and tundra bean goose (Anser serrirostris) wintering along the Yangtze River Floodplain. Based on 24 tracks obtained from 21 individuals during the spring of 2015 and 2016, we found that the Northeast China Plain is far‐out the most intensively used stopover site during migration, with geese staying for over 1 month. This region has also been intensely developed for agriculture, suggesting a causal link to the decline in East Asian waterfowl wintering in China. The protection of waterbodies used as roosting area, especially those surrounded by intensive foraging land, is critical for waterfowl survival. Over 90% of the core area used during spring migration is not protected. We suggest that future ground surveys should target these areas to confirm their relevance for migratory waterfowl at the population level, and core roosting area at critical spring‐staging sites should be integrated in the network of protected areas along the flyway. Moreover, the potential bird–human conflict in core stopover area needs to be further studied. Our study illustrates how satellite tracking combined with spatial analyses can provide crucial insights necessary to improve the conservation of declining Migratory species.
Genetic diversity of melon aphids Aphis gossypii associated with landscape features
Authors: Dong Zhaoke , Li Yifan , Zhang Zhiyong
Published: May 2018

Despite increasing evidence that landscape features strongly influence the abundance and dispersal of insect populations, landscape composition has seldom been explicitly linked to genetic structure. We conducted a genetic study of the melon aphid, Aphis gossypii, in two counties of Beijing, China during spring migration using samples from watermelon. We performed aphid genetic analysis using restriction site associated DNA sequencing (2b‐RAD) and investigated the relationship between land cover and the genetic diversity. The percentage area of land cover (cropland, vegetable, orchard, grassland, woodland) was quantified in each particular scale (ranging from 0.5 km to 3 km) and was used as a predictor variable in our generalized linear models. We found a moderate level of genetic differentiation among nine sampled populations. Geographic distance and genetic distance were not significantly associated, indicating that geographic location was not a barrier to migration. These nine populations could be clustered depending on their level of genetic diversity (high and low). The genetic diversity (Shannon’s information index) was positively correlated with grassland at the spatial scales of 1 and 2 km and negatively with orchard and vegetable at 0.5 and 1 km. Genetic diversity was best predicted by the grassland + orchard + vegetable model at a spatial scale of 1 km. Based on the method of relative weights, orchard land had the greatest relative importance, followed by grassland and vegetable land, in that order. This study contributes to our understanding of the genetic variation of aphids in agricultural landscapes.
The role of a non‐native tree in riparian vegetation expansion and channel narrowing along a dryland river
Authors: Scott Michael L. , Reynolds Lindsay V. , Shafroth Patrick B. , Spence John R.
Published: May 2018

Along rivers, native and invasive species may establish and persist on active channel bedforms as part of channel narrowing. Using historical aerial photography and dendrochronology, we quantified spatial and temporal patterns of narrowing and vegetation expansion, including native Fremont cottonwood (Populus fremontii) and non‐native Russian olive (Elaeagnus angustifolia), along the largely unregulated Escalante River in south‐western United States. Russian olive establishment was examined with respect to hydrologic and climate variables. Narrowing along the Escalante River was initiated during a mid‐20th century drought. Cottonwood rapidly colonized higher, bar surfaces between the 1950s and 1981. Small numbers of Russian olive established in moist sites during this period as the channel narrowed by nearly 80%. After 1981, there was no obvious cottonwood establishment but low channel bars and banks were rapidly colonized by Russian olive. Hydroclimate predictors were equivocal but exponential growth of this large‐seeded, shade‐tolerant species lagged its introduction by 30 years, apparently because of delayed reproductive maturity, limited seed availability, and widespread availability of favourable establishment sites following initial channel narrowing. Sediment trapping, levee formation, and modification of channel form by dense, channel‐edge bands of Russian olive progressively limited new establishment sites and by 2000, recruitment declined sharply. Our results have implications for management of non‐native tree invasions along arid‐region rivers, including identification of low, moist, active channel bars where the establishment and physical impacts of Russian olive appear to be most pronounced and where focused management efforts are likely to be most effective.
Intraspecific variation in indirect plant–soil feedbacks influences a wetland plant invasion
Authors: Allen Warwick J. , Meyerson Laura A. , Flick Andrew J. , Cronin James T.
Published: May 2018

Plant–soil feedbacks (PSFs) influence plant competition via direct interactions with pathogens and mutualists or indirectly via apparent competition/mutualisms (i.e., spillover to co‐occurring plants) and soil legacy effects. It is currently unknown how intraspecific variation inPSFs interacts with the environment (e.g., nutrient availability) to influence competition between native and invasive plants. We conducted a fully crossed multi‐factor greenhouse experiment to determine the effects ofPhragmites australisrhizosphere soil biota, interspecific competition, and nutrient availability on biomass of replicate populations from one native and two invasive lineages of common reed (P. australis) and a single lineage of native smooth cordgrass (Spartina alterniflora). Harmful soil biota consistently dominatedPSFs involving all threeP. australislineages, reducing biomass by 10%. IndirectPSFs (i.e., soil biota spillover) from the two invasiveP. australislineages reducedS. alterniflorabiomass by 7%, whereasPSFs from the nativeP. australislineage increasedS. alterniflorabiomass by 6%. Interestingly, interspecific competition andPSFs interacted to weaken their respective impacts onS. alterniflora, whereas they exerted synergistic negative effects onP. australis.Phragmites australissoil biota decreasedS. alterniflorabiomass when grown alone (i.e., a soil legacy), but increasedS. alterniflorabiomass when grown withP. australis, suggesting thatP. australisrecruits harmful generalist soil biota or facilitatesS. alternifloravia spillover (i.e., apparent mutualism). Soil biota also reduced interspecific competition impacts onS. alterniflora, although it remained competitively inferior toP. australisacross all treatments. Competitive interactions and responses to nutrients did not differ amongP. australislineages, indicating that interspecific competition and nutrient deposition may not be key drivers ofP. australisinvasion in North America. Although soil biota, interspecific competition, and nutrient availability appear to have no direct impact on the success of invasiveP. australislineages in North America, intraspecific lineage variation in indirect spillover and soil legacies fromP. australisoccur and may have important implications for co‐occurring native species and restoration of invaded habitats. Our study integrates multiple factors linked to plant invasions, highlighting that indirect interactions are likely commonplace in influencing plant community dynamics and invasion success and impacts.
Thermochemistry and Bond Nature of Oxo and Thio Ligands in Rhenium(V) Catalysts and Rhenium(VII) Intermediates: Density Functional Calculations
Authors: Ibdah Abdellatif , Alduwikat Salwa
Published: May 2018

Models of dithiolate rhenium(V)–oxo and –thio complexes and ReVII (ReVIIO2 and ReVIIOS) intermediates are studied computationally using DFT(B3LYP). The analysis of the Re–E bond (E = O, S) shows that the two lone pairs (Px, Py) on the oxo and thio ligands are strongly polarized to the ReV and ReVII centers, forming partial π bonds, which agree with the bond‐order analysis of 2 (one σ + two partial π bonds). The lone pairs on the thio ligands are less polarized than on the oxo ligand. The ReVO and ReVS bond strengths are calculated to be approximately 163.7 ± 1.8 kcal mol–1 and 123 ± 3 kcal mol–1, respectively. The ReVIIO and ReVIIS bond strengths are calculated to be 118.7 ± 1.2 kcal mol–1 and 80.5 ± 3.5 kcal mol–1, respectively. The calculated oxo– and thio–rhenium bond strengths and the thermochemistry of the OAT (oxygen‐atom transfer) cycle support that ReVIIO2 and ReVIIOS are the key intermediates in the OAT (oxygen atom transfer) and SAT (sulfur atom transfer) reactions.
Platinum Complexes with a Phosphino‐Oxime/Oximate Ligand
Authors: Francos Javier , Borge Javier , Conejero Salvador , Cadierno Victorio
Published: May 2018

The platinum(II) complex [PtCl2(COD)] (2; COD = 1,5‐cyclooctadiene) reacted with 1 and 2 equiv. of 2‐(diphenylphosphanyl)benzaldehyde oxime (1) to generate [PtCl2{κ2‐(P,N)‐2‐Ph2PC6H4CH=NOH}] (3) and [Pt{κ2‐(P,N)‐2‐Ph2PC6H4CH=NOH}2][Cl]2(4), respectively. Deprotonation of the oxime hydroxyl group of3with Na2CO3led to the selective formation of the dinuclear species (µ‐O)‐[PtCl{κ2‐(P,N)‐2‐Ph2PC6H4CH=NO}]2(5), while the related methylated derivative (µ‐O)‐[PtMe{κ2‐(P,N)‐2‐Ph2PC6H4CH=NO}]2(7) could be obtained from the direct reaction of [PtMe2(COD)] (6) with the phosphino‐oxime ligand1. In the case of4, its treatment with Na2CO3yielded complex [Pt({κ2‐(P,N)‐2‐Ph2PC6H4CH=NO}2H)][Cl] (8), as a result of the deprotonation of only one of the OH groups of4. On the other hand, contrary to what was observed with6, no deprotonation of the oxime occurred in the reaction of [PtMe3I]4(9) with1, from which the mononuclear PtIVderivativefac‐[PtIMe3{κ2‐(P,N)‐2‐Ph2PC6H4CH=NOH}] (10) was isolated. The solid‐state structures of compounds3,4,7and10were determined by X‐ray crystallography. In addition, the potential of all the synthesized complexes as catalysts for the dehydrogenative coupling of hydrosilanes with alcohols is also briefly discussed.
Asymmetric Total Synthesis and Biological Evaluation of Proapoptotic Natural Myrcene‐Derived Cyclohexenyl Chalcones
Authors: Tiamas Shelly Gapil , Audet Florian , Samra Alma Abou , Bignon Jérome , Litaudon Marc , Fourneau Christophe , Ariffin Azhar , Awang Khalijah , Desrat Sandy , Roussi Fanny
Published: May 2018

Based on a bioinspired asymmetric Diels–Alder cycloaddition using a chiral Evans oxazolidinone, the first total synthesis of both enantiomers of two myrcene‐derived cyclohexenyl chalcones, fislatifolione and fislatifolic acid, has been carried out. This strategy was also applied to the total synthesis of nicolaiodesin C. These natural products, as well as their synthetic intermediates, were evaluated by in‐vitro affinity displacement assays, based on the modulation of Bcl‐xL/Bak, Mcl‐1/Bid, and Bcl‐2‐Bim interactions. This study showed that (+)‐fislatifolic acid acts as a dual Bcl‐xL/Mcl‐1 inhibitor with micromolar activity, and that a Weinreb amide intermediate acts as an excellent Mcl‐1/Bcl‐2 dual inhibitor at the submicromolar level.
Ultrasound Guided Transversus Thoracic Plane block, Parasternal block and fascial planes hydrodissection for internal mammary post thoracotomy pain syndrome
Authors: Piraccini E. , Biondi G. , Byrne H. , Calli M. , Bellantonio D. , Musetti G. , Maitan S.
Published: May 2018

Introduction

Pectoral Nerves Block (PECS) and Serratus Plane Block (SPB) have been used to treat persistent post‐surgical pain after breast and thoracic surgery; however, they cannot block the internal mammary region, so a residual pain may occur in that region. Parasternal block (PSB) and Thoracic Transversus Plane Block (TTP) anaesthetize the anterior branches of T2‐6 intercostal nerves thus they can provide analgesia to the internal mammary region.

Methods

We describe a 60‐year‐old man suffering from right post‐thoracotomy pain syndrome with residual pain located in the internal mammary region after a successful treatment with PECS and SPB. We performed a PSB and TTP and hydrodissection of fascial planes with triamcinolone and Ropivacaine.

Results

Pain disappeared and the result was maintained 3 months later.

Discussion

This report suggests that PSB and TTP with local anaesthetic and corticosteroid with hydrodissection of fascial planes might be useful to treat a post thoracotomy pain syndrome located in the internal mammary region.

Significance

The use of Transversus Thoracic Plane and Parasternal Blocks and fascial planes hydrodissection as a novel therapeutic approach to treat a residual post thoracotomy pain syndrome even when already treated with Pectoral Nerves Block and Serratus Plane Block.
Hollow mesoporous structured molecularly imprinted polymer as adsorbent in pipette‐tip solid‐phase extraction for the determination of antiretrovirals from plasma of HIV‐infected patients
Authors: Simões Nathália Soares , de Oliveira Hanna Leijoto , da Silva Ricky Cássio Santos , Teixeira Leila Suleimara , Sales Thaís Lorenna Souza , de Castro Whocely Victor , de Paiva Maria José Nunes , Sanches Cristina , Borges Keyller Bastos
Published: May 2018

In this work a hollow mesoporous structured molecularly imprinted polymer was synthetized and used as adsorbent in pipette‐tip solid‐phase extraction for the determination of lamivudine (3TC), zidovudine (AZT) and efavirenz (EFZ) from plasma of human immunodeficiency virus (HIV) infected patients by high‐performance liquid chromatography (HPLC). All parameters that influence the recovery of the pipette tip based on hollow mesoporous molecularly imprinted polymer solid‐phase extraction (PT–HM–MIP–SPE) method were systematically studied and discussed in detail. The adsorbent material was prepared using methacrylic acid and 4‐vinylpyridine as functional monomers, ethylene glycol dimethacrylate as crosslinker, acetonitrile as solvent, 4,4′‐azobis(4‐cyanovaleric acid) as radical initiator, benzalkonium chloride as surfactant, 3TC, and AZT as templates. The simultaneous separation of 3TC, AZT and EFZ by HPLC‐UV was performed using a Gemini C18 Phenomenex® column (250 mm × 4.6 mm, 5 μm) and mobile phase consisting of acetonitrile: water pH 3.2 (68:32, v/v), flow rate of 1.0 mL/min and λ = 260 nm. The method was linear over the concentration range from 0.25 to 10 μg/mL for 3TC and EFZ, and 0.05 to 2.0 μg mL−1 for AZT, with correlation coefficients larger than 0.99 for all analytes. Recovery ± relative standard deviations (RSDs %) were 41.99 ± 2.38%, 82.29 ± 1.63%, and 83.72 ± 7.52% for 3TC, AZT, and EFZ, respectively. The RSDs and relative errors (REs) were lower than 15% for intra and interday assays. The method has been successfully applied for monitoring HIV‐infected patients outside the therapeutic dosage.
Macroeconomic forecasting with mixed data sampling frequencies: Evidence from a small open economy
Authors: Tsui Albert K. , Xu Cheng Yang , Zhang Zhaoyong
Published: May 2018

The aim of this study was to forecast the Singapore gross domestic product (GDP) growth rate by employing the mixed‐data sampling (MIDAS) approach using mixed and high‐frequency financial market data from Singapore, and to examine whether the high‐frequency financial variables could better predict the macroeconomic variables. We adopt different time‐aggregating methods to handle the high‐frequency data in order to match the sampling rate of lower‐frequency data in our regression models. Our results showed that MIDAS regression using high‐frequency stock return data produced a better forecast of GDP growth rate than the other models, and the best forecasting performance was achieved by using weekly stock returns. The forecasting result was further improved by performing intra‐period forecasting.
The characteristics and geneses of iron deposits in the Bailingshan area, Eastern Tianshan, Xinjiang, NW China
Authors: Fan Shuanghu , Chen Shu'e , Zhang Yibin , Zhang Li , Liu Lei , Yang Liuchen
Published: May 2018

The Bailingshan area of the Eastern Tianshan is rich in iron deposits, mainly magnetite and haematite. Further explorations revealed that the genesis of these two types of deposits was different. The magnetite deposits are found both in the Late Carboniferous–Permian granitoid intrusions and the surrounding rocks, composed of veined or tabular ore bodies, and controlled by fractures or interlayered sliding belts. The formations of these iron deposits are related to the injection of ore‐bearing thermal fluids from the magma in the Late Carboniferous–Permian. The sulphur isotopic characteristics indicated that the ore‐forming materials were mainly derived from the upper mantle. The haematite deposit composed of layered ore bodies hosted in the volcanic rocks of the Upper Carboniferous Dikaner Formation is related to the volcanic hydrothermal deposition.
Evaluating the impact of physicians' provision on primary healthcare: Evidence from Brazil's More Doctors Program
Authors: Fontes Luiz Felipe Campos , Conceição Otavio Canozzi , Jacinto Paulo de Andrade
Published: May 2018

This study aims to evaluate the More Doctors Program (Programa Mais Médicos) in terms of the provision of physicians, presenting estimates of its impact on hospitalization for ambulatory care sensitive conditions. The differences‐in‐differences method was used with propensity score matching (double difference matching), using 3 specifications, a falsification test, and also a dynamic endogeneity test to confirm the robustness of the results. For the application of this methodology, a panel of municipal data was constructed covering several variables related to socioeconomic, demographic, and public health infrastructure characteristics in the cities for the period from 2010 to 2016. The results show a significant reduction in hospital admissions in treated municipalities with an increasing and perceptible effect in the second year of the program.