bluuebunny/crossref_metadata_2025 huggingface dataset:
Adjusting HIV prevalence estimates for non‐participation: an application to demographic surveillance
Authors: McGovern Mark E. , Marra Giampiero , Radice Rosalba , Canning David , Newell Marie‐Louise , Bärnighausen Till
Published: November 2015

Introduction

HIV testing is a cornerstone of efforts to combat the HIV epidemic, and testing conducted as part of surveillance provides invaluable data on the spread of infection and the effectiveness of campaigns to reduce the transmission of HIV. However, participation in HIV testing can be low, and if respondents systematically select not to be tested because they know or suspect they are HIV positive (and fear disclosure), standard approaches to deal with missing data will fail to remove selection bias. We implemented Heckman‐type selection models, which can be used to adjust for missing data that are not missing at random, and established the extent of selection bias in a population‐based HIV survey in an HIV hyperendemic community in rural South Africa.

Methods

We used data from a population‐based HIV survey carried out in 2009 in rural KwaZulu‐Natal, South Africa. In this survey, 5565 women (35%) and 2567 men (27%) provided blood for an HIV test. We accounted for missing data using interviewer identity as a selection variable which predicted consent to HIV testing but was unlikely to be independently associated with HIV status. Our approach involved using this selection variable to examine the HIV status of residents who would ordinarily refuse to test, except that they were allocated a persuasive interviewer. Our copula model allows for flexibility when modelling the dependence structure between HIV survey participation and HIV status.

Results

For women, our selection model generated an HIV prevalence estimate of 33% (95% CI 27–40) for all people eligible to consent to HIV testing in the survey. This estimate is higher than the estimate of 24% generated when only information from respondents who participated in testing is used in the analysis, and the estimate of 27% when imputation analysis is used to predict missing data on HIV status. For men, we found an HIV prevalence of 25% (95% CI 15–35) using the selection model, compared to 16% among those who participated in testing, and 18% estimated with imputation. We provide new confidence intervals that correct for the fact that the relationship between testing and HIV status is unknown and requires estimation.

Conclusions

We confirm the feasibility and value of adopting selection models to account for missing data in population‐based HIV surveys and surveillance systems. Elements of survey design, such as interviewer identity, present the opportunity to adopt this approach in routine applications. Where non‐participation is high, true confidence intervals are much wider than those generated by standard approaches to dealing with missing data suggest.
The brown adipocyte protein CIDEA promotes lipid droplet fusion via a phosphatidic acid-binding amphipathic helix
Authors: Barneda David , Planas-Iglesias Joan , Gaspar Maria L , Mohammadyani Dariush , Prasannan Sunil , Dormann Dirk , Han Gil-Soo , Jesch Stephen A , Carman George M , Kagan Valerian , Parker Malcolm G , Ktistakis Nicholas T , Klein-Seetharaman Judith , Dixon Ann M , Henry Susan A , Christian Mark
Published: November 2015

Maintenance of energy homeostasis depends on the highly regulated storage and release of triacylglycerol primarily in adipose tissue, and excessive storage is a feature of common metabolic disorders. CIDEA is a lipid droplet (LD)-protein enriched in brown adipocytes promoting the enlargement of LDs, which are dynamic, ubiquitous organelles specialized for storing neutral lipids. We demonstrate an essential role in this process for an amphipathic helix in CIDEA, which facilitates embedding in the LD phospholipid monolayer and binds phosphatidic acid (PA). LD pairs are docked by CIDEA trans-complexes through contributions of the N-terminal domain and a C-terminal dimerization region. These complexes, enriched at the LD–LD contact site, interact with the cone-shaped phospholipid PA and likely increase phospholipid barrier permeability, promoting LD fusion by transference of lipids. This physiological process is essential in adipocyte differentiation as well as serving to facilitate the tight coupling of lipolysis and lipogenesis in activated brown fat.
Actin filaments target the oligomeric maturation of the dynamin GTPase Drp1 to mitochondrial fission sites
Authors: Ji Wei-ke , Hatch Anna L , Merrill Ronald A , Strack Stefan , Higgs Henry N
Published: November 2015

While the dynamin GTPase Drp1 plays a critical role during mitochondrial fission, mechanisms controlling its recruitment to fission sites are unclear. A current assumption is that cytosolic Drp1 is recruited directly to fission sites immediately prior to fission. Using live-cell microscopy, we find evidence for a different model, progressive maturation of Drp1 oligomers on mitochondria through incorporation of smaller mitochondrially-bound Drp1 units. Maturation of a stable Drp1 oligomer does not forcibly lead to fission. Drp1 oligomers also translocate directionally along mitochondria. Ionomycin, a calcium ionophore, causes rapid mitochondrial accumulation of actin filaments followed by Drp1 accumulation at the fission site, and increases fission rate. Inhibiting actin polymerization, myosin IIA, or the formin INF2 reduces both un-stimulated and ionomycin-induced Drp1 accumulation and mitochondrial fission. Actin filaments bind purified Drp1 and increase GTPase activity in a manner that is synergistic with the mitochondrial protein Mff, suggesting a role for direct Drp1/actin interaction. We propose that Drp1 is in dynamic equilibrium on mitochondria in a fission-independent manner, and that fission factors such as actin filaments target productive oligomerization to fission sites.
Origin of activated combustion in steady-state premixed burner flame with superposition of dielectric barrier discharge
Authors: Zaima Kazunori , Akashi Haruaki , Sasaki Koichi
Published: November 2015

The objective of this work is to understand the mechanism of plasma-assisted combustion in a steady-state premixed burner flame. We examined the spatiotemporal variation of the density of atomic oxygen in a premixed burner flame with the superposition of dielectric barrier discharge (DBD). We also measured the spatiotemporal variations of the optical emission intensities of Ar and OH. The experimental results reveal that atomic oxygen produced in the preheating zone by electron impact plays a key role in the activation of combustion reactions. This understanding is consistent with that described in our previous paper indicating that the production of “cold OH(A2Σ+)” via CHO + O → OH(A2Σ+) + CO has the sensitive response to the pulsed current of DBD [K. Zaima and K. Sasaki, Jpn. J. Appl. Phys. 53, 110309 (2014)].
Influence of Na2SiO3 addition on surface microstructure and cavitation damage characteristics for plasma electrolytic oxidation of Al–Mg alloy
Authors: Lee Jung-Hyung , Son Chang-Ryeon , Kim Seong-Jong
Published: November 2015

Recently, plasma electrolytic oxidation (PEO) has emerged as a promising surface modification technique to improve surface properties of Al alloys. In this study, PEO coating process for Al–Mg alloy was conducted with two different electrolyte solutions under the same electrical parameters: one was potassium hydroxide (KOH) aqueous solution, and the other involved potassium hydroxide aqueous solution with sodium silicate (Na2SiO3). The surface morphology was observed with scanning electron microscope (SEM) and elemental compositions were identified with energy dispersive spectroscopy (EDS) analysis. The chemical structures of PEO coatings were identified by X-ray diffraction analysis. Cavitation experiment was performed using ultrasonic vibratory cavitation erosion testing apparatus. Cavitation damage of PEO coatings was characterized using SEM and three-dimensional (3D) microscope. The result indicated that the surface of Al–Mg alloy were successfully modified having complete different surface morphologies by changing electrolyte composition. It was found that the surface morphology had a great influence on the cavitation damage behavior of PEO coating.
Reference genes selection for transcript normalization in kenaf (Hibiscus cannabinusL.) under salinity and drought stress
Authors: Niu Xiaoping , Qi Jianmin , Chen Meixia , Zhang Gaoyang , Tao Aifen , Fang Pingping , Xu Jiantang , Onyedinma Sandra A. , Su Jianguang
Published: November 2015

Kenaf (Hibiscus cannabinus) is an economic and ecological fiber crop but suffers severe losses in fiber yield and quality under the stressful conditions of excess salinity and drought. To explore the mechanisms by which kenaf responds to excess salinity and drought, gene expression was performed at the transcriptomic level using RNA-seq. Thus, it is crucial to have a suitable set of reference genes to normalize target gene expression in kenaf under different conditions using real-time quantitative reverse transcription-PCR (qRT-PCR). In this study, we selected 10 candidate reference genes from the kenaf transcriptome and assessed their expression stabilities by qRT-PCR in 14 NaCl- and PEG-treated samples using geNorm, NormFinder, and BestKeeper. The results indicated thatTUBαand 18S rRNA were the optimum reference genes under conditions of excess salinity and drought in kenaf. Moreover,TUBαand 18S rRNA were used singly or in combination as reference genes to validate the expression levels of WRKY28 and WRKY32 in NaCl- and PEG-treated samples by qRT-PCR. The results further proved the reliability of the two selected reference genes. This work will benefit future studies on gene expression and lead to a better understanding of responses to excess salinity and drought in kenaf.
Persistent microbial dysbiosis in preterm premature rupture of membranes from onset until delivery
Authors: Baldwin Elizabeth A. , Walther-Antonio Marina , MacLean Allison M. , Gohl Daryl M. , Beckman Kenneth B. , Chen Jun , White Bryan , Creedon Douglas J. , Chia Nicholas
Published: November 2015

Background.Preterm Premature Rupture of Membranes (PPROM) is a major leading cause of preterm births. While the cause for PPROM remains unidentified, it is anticipated to be due to subclinical infection, since a large proportion of PPROM patients display signs of chorioamnionitis. Since subclinical infections can be facilitated by dysbiosis, our goal was to characterize the vaginal microbiome and amniotic fluid discharge upon PPROM, through latency antibiotic treatment, and until delivery, to detect the presence of pathogens, microbiota alteration, and microbial response to treatment.

Methods.Enrolled subjects (15) underwent routine institutional antenatal care for PPROM, including the administration of latency antibiotics. Serial vaginal swabs were obtained from diagnosis of PPROM through delivery and the sequencing of the V3–V5 region of the 16S rRNA gene was performed for all collected samples.

Results.The results show that Lactobacilli species were markedly decreased when compared to vaginal swabs collected from uncomplicated pregnancy subjects with a matched gestational time.PrevotellaandPeptoniphiluswere the most prevalent taxa in PPROM subjects at presentation. The vaginal microbiome of the PPROM subjects varied substantially intra- and inter-subjects. Several taxa were found to be significantly reduced during and after the antibiotic treatment:Weeksella,Lachnospira,Achromobacter, andPediococcus. In contrast,PeptostreptococcusandTissierellaceae ph2displayed a significant increase after the antibiotic treatment. However, the relative abundance ofLactobacillus,Prevotella, andPeptoniphiluswas not substantially impacted during the hospitalization of the PPROM subjects. The deficiency ofLactobacillus, and constancy of known pathogenic species, such asPrevotellaandPeptoniphilusduring and after antibiotics, highlights the persistent dysbiosis and warrants further investigation into mitigating approaches.

Discussion.PPROM is responsible for one third of all preterm births. It is thought that subclinical infection is a crucial factor in the pathophysiology of PPROM because 25–40% of patients present signs of chorioamnionitis on amniocentesis. Here we sought to directly assess the bacterial content of the vagina and leaking amniotic fluid of subjects at presentation, throughout treatment and up until delivery, in order to search for common pathogens, microbiota changes, and microbial response to latency antibiotic treatment. We have found that the vaginal microbiome of PPROM subjects is highly variable and displays significant changes to treatment. However, the unchanging deficiency ofLactobacillus, and persistence of known pathogenic species, such asPrevotellaandPeptoniphilusfrom presentation, through antibiotic treatment and up until delivery, highlights the persistent dysbiosis and warrants further investigation into mitigating approaches.
Geographic variation and genetic structure in the Bahama Oriole (Icterus northropi), a critically endangered synanthropic species
Authors: Price Melissa R. , Person Carl , Hayes William K.
Published: November 2015

Bird species may exhibit unexpected population structuring over small distances, with gene flow restricted by geographic features such as water or mountains. The Bahama Oriole (Icterus northropi) is a critically endangered, synanthropic island endemic with a declining population of fewer than 300 individuals. It now remains only on Andros Island (The Bahamas), which is riddled with waterways that past studies assumed did not hinder gene flow. We examined 1,858 base pairs of mitochondrial DNA sequenced from four gene regions in 14 birds (roughly 5% of the remaining population) found on the largest land masses of Andros Island (North Andros and Mangrove Cay/South Andros). We sought to discern genetic structuring between the remaining subpopulations and its relationship to current conservation concerns. Four unique haplotypes were identified, with only one shared between the two subpopulations. Nucleotide and haplotype diversity were higher for the North Andros subpopulation than for the Mangrove Cay/South Andros subpopulation. Analysis of molecular variance (AMOVA) yielded a Wright’s fixation index (Fst) of 0.60 (PFst= 0.016), with 40.2% of the molecular variation explained by within-population differences and 59.8% by among-population differences. Based on the mitochondrial regions examined in this study, we suggest the extant subpopulations of Bahama Oriole exhibit significant population structuring over short distances, consistent with some other non-migratory tropical songbird species.
The effectiveness of sputum pH analysis in the prediction of response to therapy in patients with pulmonary tuberculosis
Authors: Masuda Makoto , Sato Takashi , Sakamaki Kentaro , Kudo Makoto , Kaneko Takeshi , Ishigatsubo Yoshiaki
Published: November 2015

Purpose.The predictive factor of response to antituberculous therapy has not been fully elucidated. Airway acidity has been thought to be a potential indicator of the bactericidal activity. Therefore, we hypothesized that monitoring airway acidity by measuring sputum pH could predict response to therapy.

Methods.A total of 47 patients having newly diagnosed, smear-positive, active pulmonary tuberculosis were enrolled between October 2011 and March 2014. Sputum samples were serially analyzed before and after treatment. Eligible patients who initiated a standard 6-month treatment were monitored for the length of time to sputum smear and culture conversion.

Results.There were 39 patients who completed a 2-month intensive phase of isoniazid, rifampicin, pyrazinamide, and ethambutol therapy followed by a 4-month continuation phase of isoniazid and rifampicin. Although factors including age, cavitation, sputum grade, and use of an acid-suppressant were associated with initial low sputum pH in univariate analysis, multivariate analysis revealed that only age ≥61 years was a statistically important factor predicting low pH value (p= 0.005). Further outcome analysis showed that initial low sputum pH before treatment was the only factor significantly associated with shorter length of time to both sputum smear and culture conversion (p= 0.034 and 0.019, respectively) independent of the effects of age, sputum bacterial load, extent of lung lesion, and cavitation. Thus, initial low sputum pH indicated favorable response to anti-tuberculosis therapy.

Conclusions.Measuring sputum pH is an easy and inexpensive way of predicting response to standard combination therapy in patients with pulmonary tuberculosis.
On the influence of poleward jet shift on shortwave cloud feedback in global climate models
Authors: Wall Casey J. , Hartmann Dennis L.
Published: November 2015

Experiments designed to separate the effect of atmospheric warming from the effect of shifts of the eddy‐driven jet on shortwave (SW) cloud feedback are performed with three global climate models (GCMs). In each model a warming simulation produces a robust SW cloud feedback dipole, with a negative (positive) feedback in the high‐latitudes (subtropics). The cloud brightening in high‐latitudes that characterizes warming simulations is not produced by jet shifts alone in any of the models, but is highly sensitive to perturbations of freezing temperature seen by the cloud microphysics scheme, indicating that thermodynamic mechanisms involving the phase of cloud condensate dominate the SW feedback at high‐latitudes. In one of the models a poleward jet shift causes significant cloud dimming throughout the midlatitudes, but in two models it does not. Differences in cloud response to jet shifts in two of the models are attributed to differences in the shallow convection parameterizations.
Combinatorial Approach to Nanoarchitectonics for Nonviral Delivery of Nucleic Acids
Authors: Molla Mijanur Rahaman , Levkin Pavel A.
Published: November 2015

Nanoparticles based on cationic polymers, lipids or lipidoids are of great interest in the field of gene delivery applications. The research on these nanosystems is rapidly growing as they hold promise to treat wide variety of human diseases ranging from viral infections to genetic disorders and cancer. Recently, combinatorial design principles have been adopted for rapid generation of large numbers of chemically diverse polymers and lipids capable of forming multifunctional nanocarriers for the use in gene delivery applications. At the same time, current high‐throughput screening systems as well as convenient cell assays and readout techniques allow for fast evaluation of cell transfection efficiencies and toxicities of libraries of novel gene delivery agents. This allows for a rapid evaluation of structure‐function relationship as well as identification of novel efficient nanocarriers for cell transfection and gene therapy. Here, the recent contribution of high‐throughput synthesis to the development of novel nanocarriers for gene delivery applications is described.
CMOS‐Technology‐Enabled Flexible and Stretchable Electronics for Internet of Everything Applications
Authors: Hussain Aftab M. , Hussain Muhammad M.
Published: November 2015

Flexible and stretchable electronics can dramatically enhance the application of electronics for the emerging Internet of Everything applications where people, processes, data and devices will be integrated and connected, to augment quality of life. Using naturally flexible and stretchable polymeric substrates in combination with emerging organic and molecular materials, nanowires, nanoribbons, nanotubes, and 2D atomic crystal structured materials, significant progress has been made in the general area of such electronics. However, high volume manufacturing, reliability and performance per cost remain elusive goals for wide commercialization of these electronics. On the other hand, highly sophisticated but extremely reliable, batch‐fabrication‐capable and mature complementary metal oxide semiconductor (CMOS)‐based technology has facilitated tremendous growth of today's digital world using thin‐film‐based electronics; in particular, bulk monocrystalline silicon (100) which is used in most of the electronics existing today. However, one fundamental challenge is that state‐of‐the‐art CMOS electronics are physically rigid and brittle. Therefore, in this work, how CMOS‐technology‐enabled flexible and stretchable electronics can be developed is discussed, with particular focus on bulk monocrystalline silicon (100). A comprehensive information base to realistically devise an integration strategy by rational design of materials, devices and processes for Internet of Everything electronics is offered.
Separation‐Free Polyaniline/TiO2 3D Hydrogel with High Photocatalytic Activity
Authors: Jiang Wenjun , Liu Yanfang , Wang Jun , Zhang Mo , Luo Wenjiao , Zhu Yongfa
Published: November 2015

A polyaniline (PANI) hydrogel with 3D network nanostructure is synthesized by polymerizing aniline. TiO2 nanoparticles are located onto the 3D matrix of the PANI hydrogel. This PANI/TiO2 composite 3D hydrogel is efficient in removing organic contaminants owing to the synergistic effect of adsorption‐enrichment and the succedent in situ photocatalytic degradation. In this process, organic contaminant is first adsorbed and enriched onto the surface of the TiO2 nanoparticles through 3D network nanostructure of PANI hydrogel. The organic contaminant is then in situ degraded. The 3D network structured PANI/TiO2 composite hydrogel has the advantage of high reactivity in nano‐sized materials and possesses the characteristics of separation‐free in bulk materials, indicating that the composite hydrogel is ease of recycling. Overall, this work provides new insights into the fabrication of hydrogel‐based nanocomposite materials and facilitates their potential application for the synergistic removal of various aquatic pollutants in the field of water purification.
Amine‐functionalized mesoporous silica: A material capable of CO2 adsorption and fast regeneration by microwave heating
Authors: Nigar Hakan , Garcia‐Baños Beatriz , Peñaranda‐Foix Felipe L. , Catalá‐Civera Jose M. , Mallada Reyes , Santamaría Jesus
Published: November 2015

The surface of ordered mesoporous (MCM‐48) silica has been subjected to covalent grafting with silane molecules containing one to three amino groups. The dielectric properties of the materials were studied in detail, and the functionalized materials were used for CO2 adsorption at room temperature, followed by regeneration under either conventional heating or microwave irradiation. It has been found that, as the intensity of functionalization with amino groups increases (from mono‐ to tri‐amino silanes) both the CO2 load and the dielectric response at microwave frequencies increase. In particular, functionalization with a tri‐amino silane derivative gave the highest CO2 adsorption and the fastest microwave heating, resulting in a fourfold acceleration of adsorbent regeneration. The grafted material was fully stable for at least 20 adsorption‐regeneration cycles, making it an ideal candidate for microwave‐swing adsorption (MWSA) processes. © 2015 American Institute of Chemical Engineers AIChE J, 62: 547–555, 2016
Cutaneous T‐cell lymphoma: 2016 update on diagnosis, risk‐stratification, and management
Authors: Wilcox Ryan A.
Published: November 2015

Disease overview: Cutaneous T‐cell lymphomas are a heterogenous group of T‐cell lymphoproliferative disorders involving the skin, the majority of which may be classified as Mycosis Fungoides (MF) or Sézary Syndrome (SS).

Diagnosis:The diagnosis of MF or SS requires the integration of clinical and histopathologic data.

Risk‐adapted therapy: TNMB (tumor, node, metastasis, blood) staging remains the most important prognostic factor in MF/SS and forms the basis for a “risk‐adapted,” multidisciplinary approach to treatment. For patients with disease limited to the skin, expectant management or skin‐directed therapies is preferred, as both disease‐specific and overall survival for these patients is favorable. In contrast, patients with advanced‐stage disease with significant nodal, visceral, or blood involvement are generally approached with biologic‐response modifiers or histone deacetylase inhibitors before escalating therapy to include systemic, single‐agent chemotherapy. In highly‐selected patients, allogeneic stem‐cell transplantation may be considered, as this may be curative in some patients. Am. J. Hematol. 91:151–165, 2016. © 2015 Wiley Periodicals, Inc.
Anionenerkennung in Wasser: aktuelle Fortschritte aus supramolekularer und makromolarer Sicht
Authors: Langton Matthew J. , Serpell Christopher J. , Beer Paul D.
Published: November 2015

Die Erkennung von Anionen in Wasser ist auch heute noch für die moderne supramolekulare Chemie eine schwierige Aufgabe, die aber für Anwendungen in Biologie, Medizin und Umweltwissenschaften unter deren gewöhnlich wässrigen Bedingungen bewältigt werden muss. Synthetische Anionenrezeptoren für wässrige Lösungen sind bislang eher die Ausnahme als die Regel. In den letzten Jahren ist aber eine Entwicklung hin zu routinemäßiger Anionenerkennung zu beobachten, die in unserem Aufsatz beleuchtet werden soll. Ein besonderer Schwerpunkt liegt bei der gezielten Verwendung des hydrophoben Effekts und von exotischen Wechselwirkungen, wie CH‐Wasserstoffbrücken und Halogenbrücken. Wir werfen auch einen Blick über das Gebiet der Erkennung durch niedermolekulare Verbindungen hinaus in den makromolekularen Bereich, in dem es aktuelle Fortschritte für die Anionenerkennung durch Biomoleküle, Polymere und Nanopartikel zu verzeichnen gibt.
Ligand‐Promoted Borylation of C(sp3)H Bonds with Palladium(II) Catalysts
Authors: He Jian , Jiang Heng , Takise Ryosuke , Zhu Ru‐Yi , Chen Gang , Dai Hui‐Xiong , Dhar T. G. Murali , Shi Jun , Zhang Hao , Cheng Peter T. W. , Yu Jin‐Quan
Published: November 2015

A quinoline‐based ligand effectively promotes the palladium‐catalyzed borylation of C(sp3)H bonds. Primary β‐C(sp3)H bonds in carboxylic acid derivatives as well as secondary C(sp3)H bonds in a variety of carbocyclic rings, including cyclopropanes, cyclobutanes, cyclopentanes, cyclohexanes, and cycloheptanes, can thus be borylated. This directed borylation method complements existing iridium(I)‐ and rhodium(I)‐catalyzed CH borylation reactions in terms of scope and operational conditions.
Peroxygenase‐Catalyzed Oxyfunctionalization Reactions Promoted by the Complete Oxidation of Methanol
Authors: Ni Yan , Fernández‐Fueyo Elena , Baraibar Alvaro Gomez , Ullrich René , Hofrichter Martin , Yanase Hideshi , Alcalde Miguel , van Berkel Willem J. H. , Hollmann Frank
Published: November 2015

Peroxygenases catalyze a broad range of (stereo)selective oxyfunctionalization reactions. However, to access their full catalytic potential, peroxygenases need a balanced provision of hydrogen peroxide to achieve high catalytic activity while minimizing oxidative inactivation. Herein, we report an enzymatic cascade process that employs methanol as a sacrificial electron donor for the reductive activation of molecular oxygen. Full oxidation of methanol is achieved, generating three equivalents of hydrogen peroxide that can be used completely for the stereoselective hydroxylation of ethylbenzene as a model reaction. Overall we propose and demonstrate an atom‐efficient and easily applicable alternative to established hydrogen peroxide generation methods, which enables the efficient use of peroxygenases for oxyfunctionalization reactions.
Binuclear Cu(II) chiral complexes: synthesis, characterization and application in enantioselective nitroaldol (Henry) reaction
Authors: Chinnaraja E. , Arunachalam R. , Choudhary Manoj K. , Kureshy R. I. , Subramanian P. S.
Published: November 2015

Enantiopure macrocyclic ligands were synthesized from (1R,2R)‐(+)‐ and (1S,2S)‐(−)‐diphenylethylenediamine with 3,3'‐methylenebis(5‐(tert‐butyl)‐2‐hydroxybenzaldehyde) and characterized. The chirality transfer and chiral inversion from ligand to copper(II) metal centre were studied using circular dichroism spectroscopy. The enantiopure binuclear copper(II) complexes (ΔΔ and ΛΛ) were used as catalysts for asymmetric nitroaldol reaction to generate β‐nitroalcohol with 88% yield and 67% enantioselectivity. Copyright © 2015 John Wiley & Sons, Ltd.
Phenolic resin‐crosslinked natural rubber/clay nanocomposites: Influence of clay loading and interfacial adhesion on strain‐induced crystallization behavior
Authors: Masa Abdulhakim , Saito Ryota , Saito Hiromu , Sakai Tadamoto , Kaesaman Azizon , Lopattananon Natinee
Published: November 2015

Nanocomposites of natural rubber (NR) and pristine clay (clay) were prepared by latex mixing, then crosslinked with phenolic resin (PhOH). For comparative study, the PhOH‐crosslinked neat NR was also prepared. Influence of clay loading (i.e., 1, 3, 5, and 10 phr) on mechanical properties and structural change of PhOH‐crosslinked NR/clay nanocomposites was studied through X‐ray diffraction (XRD), transmission electron microscopic (TEM), wide‐angle X‐ray diffraction (WAXD), tensile property measurement, and Fourier transform infrared spectroscopy (FTIR). XRD and TEM showed that the clay was partly intercalated and aggregated, and that the dispersion state of clay was non‐uniform at higher clay loading (>5 phr). From tensile test measurement, it was found that the pronounced upturn of tensile stress was observed when the clay loading was increased and a maximum tensile strength of the PhOH‐crosslinked NR/clay nanocomposites was obtained at 5 phr clay. WAXD observations showed that an increased addition of clay induced more orientation and alignment of NR chains, thereby lowering onset strain of strain‐induced crystallization and promoting crystallinity of the NR matrix during tensile deformation. FTIR investigation indicated a strong interfacial adhesion between NR matrix and clay filler through a phenolic resin bridge. This suggested that the PhOH did not only act as curative agent for crosslinking of NR, but it also worked as coupling agent for promoting interfacial reaction between NR and clay. The presence of strong interfacial adhesion was found to play an important role in the crystallization process, leading to promotion of mechanical properties of the PhOH‐crosslinked NR/clay nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43214.
CLONING, EXPRESSION, AND FUNCTIONAL ANALYSIS OF THREE ODORANT‐BINDING PROTEINS OF THE ORIENTAL FRUIT MOTH, Grapholita molesta (BUSCK) (LEPIDOPTERA: TORTRICIDAE)
Authors: Li Guang‐Wei , Zhang Yan , Li Yi‐Ping , Wu Jun‐Xiang , Xu Xiang‐Li
Published: November 2015

Odorant‐binding proteins (OBPs) act in insect olfactory processes. OBPs are expressed in the olfactory organs and serve in binding and transport of hydrophobic odorants through the sensillum lymph to olfactory receptor neurons within the antennal sensilla. In this study, three OBP genes were cloned from the antennal transcriptome database of Grapholita molesta via reverse‐transcription PCR. Recombinant GmolOBPs (rGmolOBPs) were expressed in a prokaryotic expression system and enriched via Ni ion affinity chromatography. The binding properties of the three rGmolOBPs to four sex pheromones and 30 host‐plant volatiles were investigated in fluorescence ligand‐binding assays. The results demonstrated that rGmolOBP8, rGmolOBP11, and rGmolOBP15 exhibited high binding affinities with the major sex pheromone components (E)‐8‐dodecenyl acetate, (Z)‐8‐dodecenyl alcohol, and dodecanol. The volatiles emitted from peach and pear, decanal, butyl hexanoate, and α‐ocimene, also showed binding affinities to rGmolOBP8 and rGmolOBP11. Hexanal, heptanal, and α‐pinene showed strong binding affinities to rGmolOBP15. Results of the electrophysiological recording experiments and previous behavior bioassays indicated that adult insects had strong electroantennogram and behavioral responses toward butyl hexanoate, hexanal, and heptanal. We infer that the GmolOBP8 and GmolOBP11 have dual functions in perception and recognition of host‐plant volatiles and sex pheromones, while GmolOBP15 was mainly involved in plant volatile odorants’ perception.
Silver‐Catalyzed Allylation of Ketones and Intramolecular Cyclization through Carbene Intermediates from Cyclopropenes Under Ambient Conditions
Authors: Nakano Takeo , Endo Kohei , Ukaji Yutaka
Published: November 2015

Tandem C−C bond formation was achieved through silver‐catalyzed ring‐opening of cyclopropenes via carbene intermediates. The reaction of cyclopropenes in the presence of a silver catalyst gave indene derivatives under ambient conditions. In contrast, the insertion of organozinc reagents to silver carbene or allylic cation intermediates afforded allylmetal intermediates for the tandem allylation of carbonyl compounds.
Indian summer monsoon prediction and simulation in CFSv2 coupled model
Authors: George Gibies , Rao D. Nagarjuna , Sabeerali C. T. , Srivastava Ankur , Rao Suryachandra A.
Published: November 2015

Using carefully designed coupled model experiments, we have demonstrated that the prediction skill of the all India summer monsoon rainfall (AISMR) in Climate Forecast System version 2 (CFSv2) model basically comes from the El‐Niňo Southern Oscillation‐Monsoon teleconnection. On the other hand, contrary to observations, the Indian Ocean coupled dynamics do not have a crucial role in controlling the prediction skill of the AISMR in CFSv2. We show that the inadequate representation of the Indian Ocean coupled dynamics in CFSv2 is responsible for this dichotomy. Hence, the improvement of the Indian Ocean coupled dynamics is essential for further improvement of the AISMR prediction skill in CFSv2.
On the origin of species: Factors shaping the establishment of infant's gut microbiota
Authors: van Best Niels , Hornef Mathias W. , Savelkoul Paul H. M. , Penders John
Published: November 2015

The human gut microbiota is a complex and dynamic ecosystem, which naturally lives in a symbiotic relationship with the host. Perturbations of the microbial composition (dysbiosis) and reduced diversity may promote disease susceptibility and recurrence. In contrast to the mature intestinal microbiota of healthy adults, which appears relatively stable over time, the infant's microbiome only establishes and matures during the first years of life. In this respect, early childhood seems to represent a crucial age‐window in disease prevention, since microbial diversification and maturation of the microbiome primarily occurs during this period of life. A better understanding of ecological processes and pioneer consortia in microbial development is crucial, in order to support the development of a beneficial microbiota. Various deterministic and stochastic aspects seem to shape the microbiome in early life, including maternal, environmental, and host factors. Here, we review the current understanding of the origin of pioneer bacteria and the evolutionary factors that influence the development of the gut microbiota in infants. In addition, future perspectives, including manipulating and promoting the succession of initial bacteria during infancy, will be highlighted. Birth Defects Research (Part C) 105:240–251, 2015. © 2015 Wiley Periodicals, Inc.
Preparation and Characterization of Transitional Alumina Obtained through Ammonia Treatment
Authors: Liu Yan , Jia Litao , Hou Bo , Li Debao
Published: November 2015

In this study, different aluminas were obtained by precipitating Al(NO3
)3·9H2O with different concentration of aqueous solution of ammonium carbonate. The obtained aluminas were treated by 50 (vol/vol) % ammonia via low temperature immersing and high temperature hydrothermal treatment, respectively, then, the treated aluminas were calcined again. The crystal types, morphology, textural properties, and pore distribution of the original alumina, ammonia‐treated alumina, and the second calcined alumina were studied by characterizations of X‐ray diffraction, thermogravimetric analyses, nuclear magnetic resonance, Brunauer‐Emmett‐Teller (BET), transmission electron microscopy, and so on. Several modified aluminas with specific morphology, desired pore structure, and pure crystal types were obtained, which can be used in some specific industrial application.
Simultaneous evaluation of one‐electron reducing systems and radical reactions in cells by nitroxyl biradical as probe
Authors: Araki Yoko , Koshiishi Ichiro
Published: November 2015

In the present study, a novel probe for the simultaneous evaluation of one‐electron reducing systems (electron transport chain) and one‐electron oxidizing systems (free radical reactions) in cells by electron chemical detection was developed. Six‐membered cyclic nitroxyl radicals (2,2,6,6‐tetramethylpiperidine‐1‐oxyl; TEMPO series) are sensitive to one‐electron redox systems, generating the hydroxylamine form [TEMPO(H)] via one‐electron reduction, and the secondary amine form [TEMPO(N)] via one‐electron oxidation in the presence of thiols. In contrast, the sensitivities of five‐membered cyclic nitroxyl radicals (2,2,5,5‐tetramethylpyrrolidine‐1‐oxyl; PROXYL series) to the one‐electron redox systems are comparatively low. The electron chemical detector can detect 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO), TEMPO(H) and PROXYL but not TEMPO(N). Therefore, nitroxyl biradical, TEMPO‐PROXYL, as a probe for the evaluation of one‐electron redox systems was employed. TEMPO‐PROXYL was synthesized by the conjunction of 4‐amino‐TEMPO with 3‐carboxyl‐PROXYL via the conventional dicyclohexyl carbodiimide reaction. TEMPO‐PROXYL, TEMPO(H)‐PROXYL and TEMPO(N)‐PROXYL were simultaneously quantified by HPLC with Coularray detection. Calibration curves for the quantification of TEMPO‐PROXYL, TEMPO(H)‐PROXYL and TEMPO(N)‐PROXYL were linear in the range from 80 nm to 80 μm, and the lowest quantification limit of each molecule was estimated to be <80 nm. The relative standard deviations at 0.8 and 80 μm were within 10% (n = 5). Copyright © 2015 John Wiley & Sons, Ltd.
Platelet endothelial cell adhesion molecule‐1 (PECAM1) plays a critical role in the maintenance of human vascular endothelial barrier function
Authors: Ren Qi , Ren Limin , Ren Changjie , Liu Xuefei , Dong Chun , Zhang Xinghua
Published: November 2015

Cardiovascular endothelial barrier dysfunction is associated with a number of cardiovascular diseases. This study aims to investigate the role of platelet endothelial cell adhesion molecule‐1 (PECAM1) in the maintenance of the vascular endothelial barrier integrate. Human umbilical vein endothelial cells (HUVECs) were cultured into monolayers using as an in vitro model to assess the endothelial barrier function. Knockdown of the gene of PECAM1 markedly reduced the transendothelial resistance and increased the permeability of the HUVEC monolayers. From the wild HUVECs, we detected a complex of PECAM1, claudin1, occluding and endothelial cell selective adhesion molecule (ESAM); such a complex was not detected in the PECAM1‐deficient HUVECs. Knockdown of either claudin1, or occludin, or ESAM, did not affect the formation of the tight junction (TJ) complex. Exposure to recombinant interleukin (IL)‐13 inhibited the expression of PECAM1 and down‐regulated the HUVEC monolayer barrier function. PECAM1 plays an important role in the formation of TJ complex. Copyright © 2015 John Wiley & Sons, Ltd.
N‐Acylethanolamines Bind to SIRT6
Authors: Rahnasto‐Rilla Minna , Kokkola Tarja , Jarho Elina , Lahtela‐Kakkonen Maija , Moaddel Ruin
Published: November 2015

Sirtuin 6 (SIRT6) is an NAD+‐dependent histone deacetylase enzyme that is involved in multiple molecular pathways related to aging. Initially, it was reported that SIRT6 selectively deacetylated H3K9Ac and H3K56Ac; however, it has more recently been shown to preferentially hydrolyze long‐chain fatty acyl groups over acetyl groups in vitro. Subsequently, fatty acids were demonstrated to increase the catalytic activity of SIRT6. In this study, we investigated whether a series of N‐acylethanolamines (NAEs), quercetin, and luteolin could regulate SIRT6 activity. NAEs increased SIRT6 activity, with oleoylethanolamide having the strongest activity (EC50 value of 3.1 μm). Quercetin and luteolin were demonstrated to have dual functionality with respect to SIRT6 activity; namely, they inhibited SIRT6 activity with IC50 values of 24 and 2 μm, respectively, and stimulated SIRT6 activity more than sixfold (EC50 values of 990 and 270 μm, respectively).
Costunolide induces lung adenocarcinoma cell line A549 cells apoptosis through ROS (reactive oxygen species)—mediated endoplasmic reticulum stress
Authors: Wang Zhen , Zhao Xin , Gong Xingguo
Published: November 2015

Costunolide is an active sesquiterpene lactone derived from many herbal medicines. It has a broad spectrum of bioactivities, including anti‐inflammatory and potential anti‐tumor effects. The aims of the present study were to evaluate the inhibitory effects of costunolide on A549 cell growth and to explore the underlying molecular mechanisms. Annexin V‐FITC/PI flow cytometry analysis revealed that costunolide induced apoptosis. To study the mechanism, we found that costunolide exposure activated the unfolded protein response (UPR) signaling pathways, as shown by the up‐regulation of GRP78 and IRE1α and the activation of ASK1 and JNK. Meanwhile, siRNA knockdown of IRE1α significantly attenuated costunolide‐induced apoptosis and partly restored the mitochondrial membrane potential. ER stress‐activated JNK phosphorylated Bcl‐2 at Ser70, which changes the anti‐apoptotic function of Bcl‐2, resulting in mitochondrial dysfunction and leading to mitochondrial activation of apoptosis. Furthermore, costunolide induced ROS generation, while the antioxidant N‐acetyl cysteine (NAC) effectively blocked ER stress and apoptosis activation, suggesting that ROS acts as an upstream signaling molecule in triggering ER stress and mitochondrial apoptotic pathways. Taken together, our research demonstrates that costunolide exhibits its anti‐tumor activity though inducing apoptosis, which is mediated by ER stress. We further confirm that Bcl‐2 is a key molecule connecting the ER stress and mitochondrial pathways.
Robust Zinc Complexes that Contain Pyrrolidine‐Based Ligands as Recyclable Catalysts for the Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides
Authors: Mercadé Elisabet , Zangrando Ennio , Claver Carmen , Godard Cyril
Published: November 2015

New zinc catalysts bearing ligands that contain a pyrrolidine scaffold were synthesized and tested successfully in the coupling of CO2 with terminal and internal epoxides. These catalysts provide excellent activity and total selectivity to the corresponding cyclic carbonates, even for challenging substrates such as cyclohexene oxide, trans‐1,2‐epoxybutane, and methyl epoxioleate. The robustness of the most active catalytic system was demonstrated by turnover numbers of up to 1840 for propylene oxide. The recycling of this catalytic system was performed up to five times without relevant loss of activity using this substrate.
Near‐IR BODIPY Dyes à la Carte—Programmed Orthogonal Functionalization of Rationally Designed Building Blocks
Authors: Gómez‐Durán Cesar F. A. , Esnal Ixone , Valois‐Escamilla Ismael , Urías‐Benavides Arlette , Bañuelos Jorge , López Arbeloa Iñigo , García‐Moreno Inmaculada , Peña‐Cabrera Eduardo
Published: November 2015

Herein, we report the synthesis of polyfunctional BODIPY building blocks suitable to be subjected to several reaction sequences with complete chemoselectivity, thereby allowing the preparation of complex BODIPY derivatives in a versatile and programmable manner. The reactions included the Liebeskind–Srogl cross‐coupling reaction (LSCC), nucleophilic aromatic substitution (SNAr), Suzuki, Sonogashira, and Stille couplings, and a desulfitative reduction of the MeS group. This novel synthetic protocol is a powerful route to design a library of compounds with tailored photophysical properties for advanced applications. In this context, it is noteworthy that it offers a straightforward and cost‐effective strategy to shift the BODIPY emission deep into the near‐infrared spectral region while retaining high fluorescence quantum yields as well as highly efficient and stable laser action. These new dyes outperform the lasing behaviour of dyes considered as benchmarks over the red spectral region, overcoming the important drawbacks associated with these commercial laser dyes, namely low absorption at the standard pump wavelengths (355 and 532 nm) and/or poor photostability.
A Versatile Precursor System for Supercritical Fluid Electrodeposition of Main‐Group Materials
Authors: Bartlett Philip N. , Burt Jennifer , Cook David A. , Cummings Charles Y. , George Michael W. , Hector Andrew L. , Hasan Mahboba M. , Ke Jie , Levason William , Pugh David , Reid Gillian , Richardson Peter W. , Smith David C. , Spencer Joe , Suleiman Norhidayah , Zhang Wenjian
Published: November 2015

For the first time, a versatile electrolyte bath is described that can be used to electrodeposit a wide range of p‐block elements from supercritical difluoromethane (scCH2F2). The bath comprises the tetrabutylammonium chlorometallate complex of the element in an electrolyte of 50×10−3 mol dm−3 tetrabutylammonium chloride at 17.2 MPa and 358 K. Through the use of anionic ([GaCl4]−, [InCl4]−, [GeCl3]−, [SnCl3]−, [SbCl4]−, and [BiCl4]−) and dianionic ([SeCl6]2− and [TeCl6]2−) chlorometallate salts, the deposition of elemental Ga, In, Ge, Sn, Sb, Bi, Se, and Te is demonstrated. In all cases, with the exception of gallium, which is a liquid under the deposition conditions, the resulting deposits are characterised by SEM, energy‐dispersive X‐ray analysis, XRD and Raman spectroscopy. An advantage of this electrolyte system is that the reagents are all crystalline solids, reasonably easy to handle and not highly water or oxygen sensitive. The results presented herein significantly broaden the range of materials accessible by electrodeposition from supercritical fluid and open up the future possibility of utilising the full scope of these unique fluids to electrodeposit functional binary or ternary alloys and compounds of these elements.
Large Ferrierite Crystals as Models for Catalyst Deactivation during Skeletal Isomerisation of Oleic Acid: Evidence for Pore Mouth Catalysis
Authors: Wiedemann Sophie C. C. , Ristanović Zoran , Whiting Gareth T. , Reddy Marthala V. R. , Kärger Jörg , Weitkamp Jens , Wels Bas , Bruijnincx Pieter C. A. , Weckhuysen Bert M.
Published: November 2015

Large zeolite crystals of ferrierite have been used to study the deactivation, at the single particle level, of the alkyl isomerisation catalysis of oleic acid and elaidic acid by a combination of visible micro‐spectroscopy and fluorescence microscopy (both polarised wide‐field and confocal modes). The large crystals did show the desired activity, albeit only traces of the isomerisation product were obtained and low conversions were achieved compared to commercial ferrierite powders. This limited activity is in line with their lower external non‐basal surface area, supporting the hypothesis of pore mouth catalysis. Further evidence for the latter comes from visible micro‐spectroscopy, which shows that the accumulation of aromatic species is limited to the crystal edges, while fluorescence microscopy strongly suggests the presence of polyenylic carbocations. Light polarisation associated with the spatial resolution of fluorescence microscopy reveals that these carbonaceous deposits are aligned only in the larger 10‐MR channels of ferrierite at all crystal edges. The reaction is hence further limited to these specific pore mouths.