bluuebunny/crossref_metadata_2025 huggingface dataset:
CO2‐switchable polymeric vesicle‐network structure transition induced by a hairpin‐line molecular configuration conversion
Authors: Jing Xianwu , Lu Hongsheng , Wang Baogang , Huang Zhiyu
Published: September 2016

A triblock copolymer, containing a polyethylene glycol (PEG) block and two symmetrical poly(2‐(dimethylamino)ethyl methacrylate) (PDM) blocks, was synthesized by using PEG‐based macroinitiator with copper‐mediated living radical polymerization. The conductivity tests showed that the copolymer exhibited switchable responsiveness to CO2, i.e., a relatively high conductivity of solution can be switched on and off by bubbling and removing of CO2. According to the nuclear magnetic resonance results, the CO2‐switchable conductivity variation could be attributed to protonation and deprotonation of tertiary amine groups in PDM blocks. Moreover, at a proper weight concentration 0.5%, the copolymer aqueous solution displayed a CO2‐switchable viscosity variation. Scanning electron microscopy, cryogenic transmission electron microscopy, and dynamic light scattering characterization jointly demonstrated that the viscosity variation was the result of a CO2‐switchable vesicle‐network aggregate structure transition. This structure transition can actually be attributed to a hairpin‐line molecular configuration conversion in terms of the reasonable mechanism discussion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44417.
Flexible patch‐type hydrochromic polydiacetylene sensor for human sweat pore mapping
Authors: Seo Minjeong , Park Dong‐Hoon , Park Bum Jun , Kim Jong‐Man
Published: September 2016

Owing to their stimulus‐responsive colorimetric property, polydiacetylenes (PDAs) have been extensively investigated in the context of sensor applications. Incorporation of PDAs in matrix polymers can be utilized to add additional advantageous features into these sensors, like processability, mechanical flexibility, and mass production capability. In the current investigation, a new type of hydrochromic PDA sensor, which consists of a polydiacetylene‐polyethylene oxide (PDA‐PEO) composite film, was developed. The results of the study demonstrate that the hydrochromic film, which displays a blue‐to‐red color transition upon hydration, can be used to map human sweat secreting pores. The hygroscopic PEO component of the system enables local sweat to penetrate into the sensor film. The highly π‐conjugated, imidazolium group containing PDA in the system functions as the hydrochromic material, which undergoes a blue‐to‐red transition and a corresponding fluorescence turn‐on in response to contact with a nanoliter of sweat. In response to deposition of a fingerprint, water arising from individual sweat secreting pores promotes a change that leads to formation of a discrete fluorescence microdot pattern. The most important feature of the new sensor film is mechanical flexibility that gives it with the ability to be utilized to map sweat pores located on highly curved skin surfaces, such as those found on palms, soles, backs, and faces. Accordingly, this attribute offers critical advantages in cosmetics and biomedical applications because it enables recognition of active and inactive sweat pores on curved skin surfaces where rigid or paper‐type sweat pore sensors are ineffective. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44419.
Simultaneous removal of Cd, Co, Cu, Mn, Ni and Zn from synthetic solutions on a hemp‐based felt: Experimental design
Authors: Loiacono Sonia , Morin‐Crini Nadia , Cosentino Cesare , Torri Giangiacomo , Chanet Gilles , Winterton Peter , Crini Grégorio
Published: September 2016

The potential of using a hemp‐based material in felt form as an adsorbent for removing the metals from aqueous mixtures of Cd, Co, Cu, Mn, Ni, and Zn is investigated in the present study using batch experiments at an initial pH between 4.9 and 5.2. The operating variables studied were initial metal concentration, adsorbent dosage, contact time, agitation speed, temperature, presence of NaCl, and pH. Experiments showed that this nonconventional adsorbent exhibited interesting capacities: 1 g of hemp was able to remove 7.4 mg of metals at a concentration of 25 mg/L for each metal present in 100 mL of solution. Kinetic results showed that the process was uniform and rapid: adsorption of metals reached equilibrium in 10 min. The adsorption capacities were almost independent of temperature between 25 and 50 °C and pH between 4 and 6, but dependent on the presence of electrolytes such as NaCl. Interesting results were also obtained for real polymetallic effluents. All these findings are significant for the future development of hemp‐based materials for use as bag filters for metal removal from industrial effluents. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44422.
Adsorption of hydrophilic and hydrophobic pharmaceuticals on RO/NF membranes: Identification of interactions using FTIR
Authors: Dolar Davor , Drašinac Nina , Košutić Krešimir , Škorić Irena , Ašperger Danijela
Published: September 2016

This article examines the adsorption of pharmaceuticals on reverse osmosis (RO) and nanofiltration (NF) membranes. The membranes were characterized in terms of Fourier transformation infrared (FTIR) spectra, surface charge, hydrophobicity, pore size distribution, and roughness. Five pharmaceuticals were used to determine their rejection and possible interactions with the membranes. Albendazole, a hydrophobic pharmaceutical, adsorbed on the NF (NF270) and RO (XLE) membranes. FTIR spectra showed significant changes (new peaks/bonds) on the membranes, confirming that adsorption plays an important role in the overall mechanism of rejection in the case of hydrophobic compounds. Hydrophilic pharmaceuticals (sulfaguanidine, trimethoprim, hydrocortisone, and procaine) did not adsorb on the XLE membrane, showing that size exclusion and electrostatic repulsion were both dominant removal mechanisms. This article gives new insights into NF membranes in the treatment of hydrophilic compounds. The results clearly show the adsorption of hydrophilic compounds on the NF membranes since H‐bonds and π–π interactions were observed on their FTIR spectra. Therefore, both the hydrophobic and the hydrophilic adsorption have to be taken into account when considering the removal mechanism, especially in the case of NF membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44426.
Identification and Characterization of Small‐Molecule Inhibitors to Selectively Target the DFG‐in over the DFG‐out Conformation of the B‐Raf Kinase V600E Mutant in Colorectal Cancer
Authors: Yao Huixiang , Sun Qun , Zhu Jinshui
Published: September 2016

V600E is the most common mutation in the B‐Raf kinase domain and the B‐RafV600E mutant has been recognized as an attractive target of colorectal cancer. Here, the structural dynamics of V600E‐induced conformational conversion in the B‐Raf activation loop (A‐loop) was characterized in detail using a computational simulation strategy. The simulations revealed that the V600E mutation would induce A‐loop flipping from DFG‐out to DFG‐in, and the approved B‐Raf inhibitor vemurafenib exhibits strong selectivity for the mutant over the wild‐type kinase. The selectivity is closely associated with the kinase conformation, which can be influenced directly by the V600E mutation. The molecular structure of vemurafenib was applied to a chemical similarity search against a large library of drug/lead‐like compounds, from which three hits with high structural similarity were identified, and their inhibitory activities against both the wild‐type and mutant kinases were measured by in vitro kinase assay, from which two compounds were determined to possess higher selectivity for the B‐RafV600E mutant than for the wild type (5.2‐ and 3.1‐fold, respectively). They can potently inhibit the kinase mutant with IC50 = 54 and 76 nM, respectively. Structural analysis suggested that specific noncovalent interactions play a crucial role in the selectivity of B‐Raf inhibitors.
A distributed cellulosic biorefinery system in the US Midwest based on corn stover
Authors: Kim Seungdo , Dale Bruce E.
Published: September 2016

Corn stover supply chains in a distributed biorefinery system are explored. The distributed cellulosic biorefinery uses pre‐processed and densified cellulosic feedstock from a geographically separated facility (a depot) as raw material. A network of small‐scale depot facilities supplies pre‐processed feedstock to a distributed biorefinery. Depot facilities are assumed to be located at existing grain elevators, while distributed biorefineries are located adjacent to coal‐fired power plants in areas with high gasoline consumption (urban areas) in the Midwest. The county level corn stover projections in 2022 by the US Billion‐Ton Update report (2011) are used to estimate ethanol selling price and greenhouse gas (GHG) emissions of the ethanol fuel. The supply chain for each distributed biorefinery is determined by minimizing the ethanol selling price. Approximately ten distributed biorefineries based on corn stover could be established in the Midwest. Over 700 individual depot facilities participate in supplying the distributed biorefinery systems which collectively can produce greater than 12 hm3 of ethanol (3.3 billion gallons) per year. Ethanol selling price in the distributed system ranges from US$0.66 to US$1.03 per liter. Some distributed biorefineries are economically competitive with a centralized biorefinery. However, not every region can support a distributed biorefinery system due to inadequate corn stover availability. Cradle‐to‐gate GHG emissions of ethanol in the distributed systems are 22.1–46.6 g CO2 per MJ. The external energy consumption in the depot facilities is the major GHG source. Optimizing process energy use in the depot facility is required to reduce both operation costs and GHG emissions. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
Short‐term and long‐term effects of acute kidney injury in chronic kidney disease patients: A longitudinal analysis
Authors: Asar Özgür , Ritchie James , Kalra Philip A. , Diggle Peter J.
Published: September 2016

We use data from an ongoing cohort study of chronic kidney patients at Salford Royal NHS Foundation Trust, Greater Manchester, United Kingdom, to investigate the influence of acute kidney injury (AKI) on the subsequent rate of change of kidney function amongst patients already diagnosed with chronic kidney disease (CKD). We use a linear mixed effects modelling framework to enable estimation of both acute and chronic effects of AKI events on kidney function. We model the fixed effects by a piece‐wise linear function with three change‐points to capture the acute changes in kidney function that characterise an AKI event, and the random effects by the sum of three components: a random intercept, a stationary stochastic process with Matérn correlation structure, and measurement error. We consider both multivariate Normal and multivariatetversions of the random effects. For either specification, we estimate model parameters by maximum likelihood and evaluate the plug‐in predictive distributions of the random effects given the data. We find that following an AKI event the average long‐term rate of decline in kidney function is almost doubled, regardless of the severity of the event. We also identify and present examples of individual patients whose kidney function trajectories diverge substantially from the population‐average.
Spliced analogues of trypsin inhibitor SFTI‐1 and their application for tracing proteolysis and delivery of cargos inside the cells
Authors: Filipowicz Magdalena , Ptaszyńska Natalia , Olkiewicz Katarzyna , Dębowski Dawid , Ćwikłowska Kamila , Burster Timo , Pikuła Michał , Krzystyniak Adam , Łęgowska Anna , Rolka Krzysztof
Published: September 2016

A series of analogues of trypsin inhibitor SFTI‐1 were designed and synthesized to monitor peptide splicing. In the middle part of the SFTI‐1 analogues, which is released upon incubation with proteinase, the RGD sequence or an acceptor of fluorescence for FRET was introduced. The results of studies with trypsin confirmed that the designed analogues underwent peptide splicing. Furthermore, we showed that a FRET displaying SFTI‐1 analogue was internalized into the HaCaT keratinocytes, where it was degraded. Therefore, both proteolysis and the reduction of the disulfide bridge of the peptide took place. As a result, such analogues are a convenient tool to trace the proteolytic activity inside the cell. However, the cytotoxicity of SFTI‐1 analogues grafted with the RGD sequence did not correlate with their susceptibility to peptide splicing. Nevertheless, these peptides were slightly more active than the reference peptide (GRGDNP). Interestingly, one of the analogues assigned as [desSer6]VI, under experimental conditions, appeared significantly more cytotoxic towards cancer cells U87‐MG in contrast to the reference peptide.
Copper‐Modified Gold Nanoparticles as Highly Selective Catalysts for Glycerol Electro‐Oxidation in Alkaline Solution
Authors: Thia Larissa , Xie Mingshi , Liu Zhaolin , Ge Xiaoming , Lu Yizhong , Fong Wenmei Eileen , Wang Xin
Published: September 2016

The C3 selectivity of carbon‐supported Au nanoparticles for glycerol electro‐oxidation was significantly enhanced by the interaction of Au with electro‐deposited Cu species. Notably, the C3 selectivity of supported Au nanoparticles doubled after 90 min of Cu electro‐deposition at +0.015 V. This result was obtained if glycerol electro‐oxidation was performed at +0.1 V for 2 h. The most selective catalysts contained an Au+ species that was generated by an interaction between Au and electro‐deposited Cu2O. The presence of Au+ increased the selectivity to glycerate and tartronate and suppressed C−C bond cleavage to glycolate and formate simultaneously.
Surfactant‐Free Palladium Nanoparticles Encapsulated in ZIF‐8 Hollow Nanospheres for Size‐Selective Catalysis in Liquid‐Phase Solution
Authors: Wang Xiaoshi , Li Mingyu , Cao Changyan , Liu Chang , Liu Jian , Zhu Yanan , Zhang Sidi , Song Weiguo
Published: September 2016

Encapsulation of surfactant‐free Pd nanoparticles (NPs) in the metal–organic framework material ZIF‐8 hollow nanospheres was achieved. Pd@ZIF‐8 hollow nanospheres showed excellent size‐selective catalytic properties in the liquid‐phase hydrogenation of olefins. As a result of the uniform pore size of the ZIF‐8 shell (apertures of 3.4 Å), the catalyst showed high activity for the hydrogenation of 1‐hexene (1.9×8.2 Å) but very low activity for larger molecules such as cis‐cyclooctene (5.3×5.5 Å), trans‐stilbene (4.2×11.3 Å), and triphenylethylene (9.1×9.2 Å). Other surfactant‐free noble‐metal nanoparticles could also be employed to produce NPs@MOFs for catalysis.
Facile Strategy to Fabricate Uniform Black TiO2 Nanothorns/Graphene/Black TiO2 Nanothorns Sandwichlike Nanosheets for Excellent Solar‐Driven Photocatalytic Performance
Authors: Zhang Xiangcheng , Wang Jianan , Hu Weiyao , Zhang Kaifu , Sun Bojing , Tian Guohui , Jiang Baojiang , Pan Kai , Zhou Wei
Published: September 2016

Uniform black TiO2 nanothorns/graphene/black TiO2 nanothorns sandwichlike nanosheets (denoted as G@BTN) are fabricated through facile solvothermal approach and subsequent surface hydrogenation, in which the black TiO2 nanothorns vertically grow on the surface of two sides of graphene and form the sandwichlike structure. The rational control of hydrolysis and condensation of Ti precursors results in a uniform coating of amorphous TiO2 seeds, which then vertically grow in TiO2 nanothorns. After surface hydrogenation, the resultant G@BTN materials, with uniform sandwichlike configuration and narrow band gap of approximately 2.81 eV, can extend the photoresponse from the ultraviolet to the visible‐light region and exhibit an excellent solar‐driven photocatalytic performance for the degradation of the highly toxic pesticide atrazine (99 %). The first‐order rate constant (k) of G@BTN (0.863 h−1) is about three times as high as that of black TiO2 nanothorns (0.287 h−1), which implies the significant role of the introduction of graphene for improving the photocatalytic performance. The high solar‐driven photocatalytic performance is ascribed to the formed Ti3+ in frameworks and surface disorders enhancing the absorption of solar light, and the sandwichlike structure favoring the separation and transportation of photogenerated charge carriers.
Penalized eigendecompositions: motivations from domain adaptation for calibration transfer
Authors: Andries Erik
Published: September 2016

Maintaining multivariate calibrations involves keeping models developed on an instrument applicable to predicting new samples over time. Sometimes, a primary instrument model is needed to predict samples measured on secondary instruments. This situation is referred to as calibration transfer. Sometimes, a primary instrument model is needed to predict samples that have acquired new spectral features (chemical, physical, and environmental influences) over time. This situation is referred to as calibration maintenance. Calibration transfer and maintenance problems have a long history and are well studied in chemometrics and spectroscopy. In disciplines outside of chemometrics, particularly computer vision, calibration transfer and maintenance problems are more recent phenomena, and these problems often go under the umbrella term domain adaptation. Over the past decade, domain adaptation has demonstrated significant successes in various applications such as visual object recognition. Since domain adaptation already constitutes a large area of research in computer vision and machine learning, we narrow our scope and report on penalty‐based eigendecompositions, a class of domain adaptation methods that has its motivational roots in linear discriminant analysis. We compare these approaches against chemometrics‐based approaches using several benchmark chemometrics data sets.
Thermal Behavior of d‐Ribose Adsorbed on Silica: Effect of Inorganic Salt Coadsorption and Significance for Prebiotic Chemistry
Authors: Akouche Mariame , Jaber Maguy , Zins Emilie‐Laure , Maurel Marie‐Christine , Lambert Jean‐Francois , Georgelin Thomas
Published: September 2016

Understanding ribose reactivity is a crucial step in the “RNA world” scenario because this molecule is a component of all extant nucleotides that make up RNA. In solution, ribose is unstable and susceptible to thermal destruction. We examined how ribose behaves upon thermal activation when adsorbed on silica, either alone or with the coadsorption of inorganic salts (MgCl2, CaCl2, SrCl2, CuCl2, FeCl2, FeCl3, ZnCl2). A combination of 13C NMR, in situ IR, and TGA analyses revealed a variety of phenomena. When adsorbed alone, ribose remains stable up to 150 °C, at which point ring opening is observed, together with minor oxidation to a lactone. All the metal salts studied showed specific interactions with ribose after dehydration, resulting in the formation of polydentate metal ion complexes. Anomeric equilibria were affected, generally favoring ribofuranoses. Zn2+ stabilized ribose up to higher temperatures than bare silica (180 to 200 °C). Most other cations had an adverse effect on ribose stability, with ring opening already upon drying at 70 °C. In addition, alkaline earth cations catalyzed the dehydration of ribose to furfural and, to variable degrees, its further decarbonylation to furan. Transition‐metal ions with open d‐shells took part in redox reactions with ribose, either as reagents or as catalysts. These results allow the likelihood of prebiotic chemistry scenarios to be evaluated, and may also be of interest for the valorization of biomass‐derived carbohydrates by heterogeneous catalysis.
Development of a Terpenoid Alkaloid‐like Compound Library Based on the Humulene Skeleton
Authors: Kikuchi Haruhisa , Nishimura Takehiro , Kwon Eunsang , Kawai Junya , Oshima Yoshiteru
Published: September 2016

Many natural terpenoid alkaloid conjugates show biological activity because their structures contain both sp3‐rich terpenoid scaffolds and nitrogen‐containing alkaloid scaffolds. However, their biosynthesis utilizes a limited set of compounds as sources of the terpenoid moiety. The production of terpenoid alkaloids containing various types of terpenoid moiety may provide useful, chemically diverse compound libraries for drug discovery. Herein, we report the construction of a library of terpenoid alkaloid‐like compounds based on Lewis‐acid‐catalyzed transannulation of humulene diepoxide and subsequent sequential olefin metathesis. Cheminformatic analysis quantitatively showed that the synthesized terpenoid alkaloid‐like compound library has a high level of three‐dimensional‐shape diversity. Extensive pharmacological screening of the library has led to the identification of promising compounds for the development of antihypolipidemic drugs. Therefore, the synthesis of terpenoid alkaloid‐like compound libraries based on humulene is well suited to drug discovery. Synthesis of terpenoid alkaloid‐like compounds based on several natural terpenoids is an effective strategy for producing chemically diverse libraries.
The moderating effect of demographic characteristics on the relationship between strategic capabilities and firm performance in women‐owned entrepreneurial ventures in Nairobi, Kenya
Authors: Kimosop Joyce , Korir Michael , White Margaret
Published: September 2016

This study is motivated by the need to understand the determinants of performance in women‐owned enterprises. We examine the relationship between strategic capabilities and firm performance with demographic characteristics as moderators in women‐owned enterprises in Nairobi, Kenya. Results show that strategic capabilities have a significant effect on the overall performance. Further, IT capabilities and technological capabilities have a positive and significant relationship with performance. Only age has a negative and significant moderating effect. We recommend enhancement of technological capabilities among women entrepreneurs so that they can better direct their capabilities toward firm performance. Copyright © 2016 ASAC. Published by John Wiley & Sons, Ltd.
Bubble formation regimes during gas injection into a liquid cross flow in a conduit
Authors: Balzán Miguel A. , Sanders R. Sean , Fleck Brian A.
Published: September 2016

A study was performed to characterize the different bubble formation regimes that occur during the process of gas jet injection into a liquid cross flow in a conduit. Air was injected perpendicularly into a turbulent, fully developed water flow circulating through a 12.7 mm square channel. Three different gas injectors, with diameters of 0.27 mm, 0.52 mm, and 1.59 mm were used. The bulk water velocity values ranged between 1.1 and 4.3 m/s. The effects that the gas injection velocity, liquid mean velocity, and injection gas injection diameter have on the process of bubble generation were investigated. A high‐speed visualization technique was used to determine the regimes near the gas inlet region. Four distinct regimes were identified: Single Bubbling (SB), Pulse (P), Elongated Jetting (EJ), and Atomizing Jetting (AJ). It was observed that the shift between regimes occurs gradually, producing the need to identify transitional regions: SBP and PTJ. Sets of independent dimensionless variables were used to categorize the proposed regimes using bubble formation maps. It was determined that the injection diameter plays a primary role in jet formation: as the injection diameter increased, the observable number of regimes decreased, indicating a more stable and continuous process of bubble generation. Empirical correlations that delimit the boundaries between ordered and chaotic bubble generation are presented.
In vivo and ex vivo 19‐fluorine magnetic resonance imaging and spectroscopy of beta‐cells and pancreatic islets using GLUT‐2 specific contrast agents
Authors: Liang Sayuan , Louchami Karim , Kolster Hauke , Jacobsen Anna , Zhang Ying , Thimm Julian , Sener Abdullah , Thiem Joachim , Malaisse Willy , Dresselaers Tom , Himmelreich Uwe
Published: September 2016

The assessment of the β‐cell mass in experimental models of diabetes and ultimately in patients is a hallmark to understand the relationship between reduced β‐cell mass/function and the onset of diabetes. It has been shown before that the GLUT‐2 transporter is highly expressed in both β‐cells and hepatocytes and that D‐mannoheptulose (DMH) has high uptake specificity for the GLUT‐2 transporter. As 19‐fluorine MRI has emerged as a new alternative method for MRI cell tracking because it provides potential non‐invasive localization and quantification of labeled cells, the purpose of this project is to validate β‐cell and pancreatic islet imaging by using fluorinated, GLUT‐2 targeting mannoheptulose derivatives (19FMH) both in vivo and ex vivo. In this study, we confirmed that, similar to DMH, 19FMHs inhibit insulin secretion and increase the blood glucose level in mice temporarily (approximately two hours). We were able to assess the distribution of 19FMHs in vivo with a temporal resolution of about 20 minutes, which showed a quick removal of 19FMH from the circulation (within two hours). Ex vivo MR spectroscopy confirmed a preferential uptake of 19FMH in tissue with high expression of the GLUT‐2 transporter, such as liver, endocrine pancreas and kidney. No indication of further metabolism was found. In summary, 19FMHs are potentially suitable for visualizing and tracking of GLUT‐2 expressed cells. However, current bottlenecks of this technique related to the quick clearance of the compound and relative low sensitivity of 19F MRI need to be overcome. Copyright © 2016 John Wiley & Sons, Ltd.
Benefit‐Risk Analysis for Decision‐Making: An Approach
Authors: Raju GK , Gurumurthi K , Domike R
Published: September 2016

The analysis of benefit and risk is an important aspect of decision‐making throughout the drug lifecycle. In this work, the use of a benefit‐risk analysis approach to support decision‐making was explored. The proposed approach builds on the qualitative US Food and Drug Administration (FDA) approach to include a more explicit analysis based on international standards and guidance that enables aggregation and comparison of benefit and risk on a common basis and a lifecycle focus. The approach is demonstrated on six decisions over the lifecycle (e.g., accelerated approval, withdrawal, and traditional approval) using two case studies: natalizumab for multiple sclerosis (MS) and bedaquiline for multidrug‐resistant tuberculosis (MDR‐TB).
Pricing and reimbursement experiences and insights in the European Union and the United States: Lessons learned to approach adaptive payer pathways
Authors: Faulkner SD , Lee M , Qin D , Morrell L , Xoxi E , Sammarco A , Cammarata S , Russo P , Pani L , Barker R
Published: September 2016

Earlier patient access to beneficial therapeutics that addresses unmet need is one of the main requirements of innovation in global healthcare systems already burdened by unsustainable budgets. “Adaptive pathways” encompass earlier cross‐stakeholder engagement, regulatory tools, and iterative evidence generation through the life cycle of the medicinal product. A key enabler of earlier patient access is through more flexible and adaptive payer approaches to pricing and reimbursement that reflect the emerging evidence generated.
The Influence of Water Vapor on the Stability and Processing of Hybrid Perovskite Solar Cells Made from Non‐Stoichiometric Precursor Mixtures
Authors: Petrus Michiel L. , Hu Yinghong , Moia Davide , Calado Philip , Leguy Aurélien M. A. , Barnes Piers R. F. , Docampo Pablo
Published: September 2016

We investigated the influence of moisture on methylammonium lead iodide perovskite (MAPbI3) films and solar cells derived from non‐stoichiometric precursor mixtures. We followed both the structural changes under controlled air humidity through in situ X‐ray diffraction, and the electronic behavior of devices prepared from these films. A small PbI2 excess in the films improved the stability of the perovskite compared to stoichiometric samples. We assign this to excess PbI2 layers at the perovskite grain boundaries or to the termination of the perovskite crystals with Pb and I. In contrast, the MAI‐excess films composed of smaller perovskite crystals showed increased electronic disorder and reduced device performance owing to poor charge collection. Upon exposure to moisture followed by dehydration (so‐called solvent annealing), these films recrystallized to form larger, highly oriented crystals with fewer electronic defects and a remarkable improvement in photocurrent and photovoltaic efficiency.
Oxytocin modulation of neural circuits for social behavior
Authors: Marlin Bianca J. , Froemke Robert C.
Published: September 2016

Oxytocin is a hypothalamic neuropeptide that has gained attention for the effects on social behavior. Recent findings shed new light on the mechanisms of oxytocin in synaptic plasticity and adaptively modifying neural circuits for social interactions such as conspecific recognition, pair bonding, and maternal care. Here, we review several of these newer studies on oxytocin in the context of previous findings, with an emphasis on social behavior and circuit plasticity in various brain regions shown to be enriched for oxytocin receptors. We provide a framework that highlights current circuit‐level mechanisms underlying the widespread action of oxytocin. © 2016 Wiley Periodicals, Inc. Develop Neurobiol 77: 169–189, 2017
Emissions of methane from northern peatlands: a review of management impacts and implications for future management options
Authors: Abdalla Mohamed , Hastings Astley , Truu Jaak , Espenberg Mikk , Mander Ülo , Smith Pete
Published: September 2016

Northern peatlands constitute a significant source of atmospheric methane (CH4). However, management of undisturbed peatlands, as well as the restoration of disturbed peatlands, will alter the exchange of CH4 with the atmosphere. The aim of this systematic review and meta‐analysis was to collate and analyze published studies to improve our understanding of the factors that control CH4 emissions and the impacts of management on the gas flux from northern (latitude 40° to 70°N) peatlands. The analysis includes a total of 87 studies reporting measurements of CH4 emissions taken at 186 sites covering different countries, peatland types, and management systems. Results show that CH4 emissions from natural northern peatlands are highly variable with a 95% CI of 7.6–15.7 g C m−2 year−1 for the mean and 3.3–6.3 g C m−2 year−1 for the median. The overall annual average (mean ± SD) is 12 ± 21 g C m−2 year−1 with the highest emissions from fen ecosystems. Methane emissions from natural peatlands are mainly controlled by water table (WT) depth, plant community composition, and soil pH. Although mean annual air temperature is not a good predictor of CH4 emissions by itself, the interaction between temperature, plant community cover, WT depth, and soil pH is important. According to short‐term forecasts of climate change, these complex interactions will be the main determinant of CH4 emissions from northern peatlands. Drainage significantly (p < .05) reduces CH4 emissions to the atmosphere, on average by 84%. Restoration of drained peatlands by rewetting or vegetation/rewetting increases CH4 emissions on average by 46% compared to the original premanagement CH4 fluxes. However, to fully evaluate the net effect of management practice on the greenhouse gas balance from high latitude peatlands, both net ecosystem exchange (NEE) and carbon exports need to be considered.
Sexual function of patients with heart failure: facts and numbers
Authors: Jaarsma Tiny
Published: September 2016

Approximately 60% to 87% of patients with heart failure (HF) report sexual problems, and numbers as low as 31% of HF patients younger than 70 have normal sexual function. When compared with healthy elders, the amount of perceived sexual dysfunction might be similar (around 56%), but patients with HF are reporting more erectile dysfunction (ED) and also perceive that their HF symptoms (20%) or HF medication (10%) is the cause for their problems. The prevalence of ED is highly prevalent in men with cardiac disease and reported in up to 81% of cardiac patients, compared with 50% in the general older population. In total 25–76% of women with HF report sexual problems or concerns.

The physical effort related to sexual activity in cardiac patients can be compared to mild to moderate physical activity. The related energy expenditure of sexual activity falls in the range of three to five metabolic units (METs), which can be compared to the energy needed to climb three flights of stairs, general housework, or gardening.

Information about sexual activity is often overlooked by health care professionals treating HF patients. Advice and counselling about this subject are needed to decrease worries of patients and partners, avoid skipping medication because of fear for side effects, or prevent inappropriate use of potency enhancing drugs or herbs.
Rewiring cellular metabolism via the AKT/mTOR pathway contributes to host defence against Mycobacterium tuberculosis in human and murine cells
Authors: Lachmandas Ekta , Beigier‐Bompadre Macarena , Cheng Shih‐Chin , Kumar Vinod , van Laarhoven Arjan , Wang Xinhui , Ammerdorffer Anne , Boutens Lily , de Jong Dirk , Kanneganti Thirumala‐Devi , Gresnigt Mark S. , Ottenhoff Tom H.M. , Joosten Leo A.B. , Stienstra Rinke , Wijmenga Cisca , Kaufmann Stefan H.E. , van Crevel Reinout , Netea Mihai G.
Published: September 2016

Cells in homeostasis metabolize glucose mainly through the tricarboxylic acid cycle and oxidative phosphorylation, while activated cells switch their basal metabolism to aerobic glycolysis. In this study, we examined whether metabolic reprogramming toward aerobic glycolysis is important for the host response to Mycobacterium tuberculosis (Mtb). Through transcriptional and metabolite analysis we show that Mtb induces a switch in host cellular metabolism toward aerobic glycolysis in human peripheral blood mononuclear cells (PBMCs). The metabolic switch is TLR2 dependent but NOD2 independent, and is mediated in part through activation of the AKT‐mTOR (mammalian target of rapamycin) pathway. We show that pharmacological inhibition of the AKT/mTOR pathway inhibits cellular responses to Mtb both in vitro in human PBMCs, and in vivo in a model of murine tuberculosis. Our findings reveal a novel regulatory layer of host responses to Mtb that will aid understanding of host susceptibility to Mtb, and which may be exploited for host‐directed therapy.
Influence of partial pork backfat replacement by fish oil on nutritional and technological properties of liver pâté
Authors: Domínguez Rubén , Pateiro Mirian , Sichetti Munekata Paulo Eduardo , Bastianello Campagnol Paulo Cezar , Lorenzo José M.
Published: September 2016

The effect of pork backfat replacement by fish oil (with high content ofn‐3 long chain fatty acids) on proximate composition, physicochemical properties (pH, color, and texture parameters), nutritional properties (fatty acid profile and nutritional indices), and oxidative stability of liver pâté was assessed. For the present study, three different batches were manufactured: control (CO) with 100% of pork backfat and FO50 and FO75 where the pork backfat was replaced with 50 and 75% by fish oil, respectively. The fat replacement by fish oil was accompanied by an increase in fat and cholesterol content, and a decrease in moisture and protein levels. Color parameters were significantly (P < 0.05) affected by the partial replacement of pork backfat by fish oil, the FO75 batches presented the highest redness, and yellowness values. On the other hand, hardness and gumminess decreased (P < 0.001) as increased fish oil addition. The SFA amount in the modified pâté decreased by 3.2–4.6% and PUFA content increased by 6.2–9.5% compared to the CO treatment. Finally, the highest lipid oxidation‐derived volatiles obtained in modified pâté could be related with the different levels of polyunsaturation among batches.

Practical applications:Lipid modification of pâté by substitution of pork backfat with fish oil has been shown to be a good strategy to improve their nutritional quality. A decrease in saturated fats and an increase in unsaturated fats when pork backfat was partially replaced by fish oil were obtained. This change could be considered as the main factor responsible of the lowest values of hardness achieved in modified pâtés. This study contributed to prepare a better product for final consumers who are become increasingly health conscious and demand high quality food products.

The effect of pork backfat replacement by fish oil on chemical composition, nutritional properties, and oxidative stability of liver pâté was studied. Lipid modification of pâté has been shown to be a good strategy to improve their nutritional quality (decrease saturated fats and increase unsaturated fats). However, the high level of polyunsaturation increase lipid oxidation‐derived volatiles. Finally, this study contributed to prepare a better product for final consumers who are become increasingly health conscious and demand high quality food products.
A New Route for the Enzymeless Trace Level Detection of Creatinine Based on Reduced Graphene Oxide/Silver Nanocomposite Biosensor
Authors: Viswanath K. Balaji , Devasenathipathy Rajkumar , Wang Sea‐Fue , Vasantha V. S.
Published: September 2016

Renal insufficiencies and muscle diseases can be easily identified from the concentration of creatinine in blood and urine. Although various chemical sensors have been developed to detect creatinine, selectivity and robustness of chemical sensors are the main obstacles for many researchers. To overcome these difficulties, finding a suitable chemical biosensor with long‐term stability, low cost, high sensitivity and selectivity for the detection of creatinine is immensely desirable. Herein, we have developed a novel enzymeless creatinine biosensor for the trace level detection of creatinine using reduced graphene oxide (RGO)/ silver nanoparticles (AgNPs) which was prepared by simple one step electrochemical potentiodyanamic method. The anodic peak current of AgNPs gradually decreased when the concentration of creatinine was increased. Based on the decrease of anodic peak current, we have introduced a new platform for the detection of creatinine. The adsorption of creatinine on AgNPs was confirmed by various techniques. The newly proposed biosensor exhibited a very low detection limit of 0.743 pM with linear range from 10 pM to 120 pM. The demonstrated sensor can detect creatinine even in the presence of other interfering biomolecules such as glucose, ascorbic acid, uric acid, urea and creatine.
Binderless Solution Processed Zn Doped Co3O4 Film on FTO for Rapid and Selective Non‐enzymatic Glucose Detection
Authors: Chowdhury Mahabubur , Cummings Franscious , Kebede Mesfin , Fester Veruscha
Published: September 2016

A simple solution based deposition process has been used to fabricate Zn doped Co3O4 electrode as an electrocatalyst for non‐enzymatic oxidation of glucose. XRD, HRTEM, SEM, EELS, AFM, EIS was used to characterise the electrode. The addition of Zn as dopant on Co3O4 resulted in enhanced electrochemical performance of Zn:Co3O4 material compared to pristine Co3O4 due to increased charge transferability. The as prepared electrode showed fast response (<7 s) time, good sensitivity (193 μA mM−1 cm−2) in the linear range of 5 μM–0.62 mM, good selectivity towards glucose at a relatively lower applied potential of +0.52 V in 0.1 M NaOH solution. A detection limit of ∼2 μM was measured for the Zn:Co3O4 electrode. The applied fabrication method resulted in good inter and intra electrode reproducibility as was shown by the lower relative standard deviation values (R.S.D). The electrode retained 70 % of initial current response after 30 days. Although the as prepared Zn:Co3O4 electrodes did not result in highest reported sensitivity, and lowest limit of detection; the ease of fabrication and scalability of production, good inter and intra electrode reproducibility makes it a potential candidate for commercial application as glucose sensor.
A New Approach for Decreasing the Detection Limit of Gentamicin Ion‐selective Electrodes by Incorporation of Multiwall Carbon Nanotubes (MWCNTs)/Lipophilic Anionic Additives
Authors: Khalil M. M. , El‐aziz G. M. Abed
Published: September 2016

Two novel carbon paste electrodes based on gentamicin‐reineckate (GNS‐RN)/multiwall carbon nanotubes (MWCNTs)/sodium tetraphenyl borate (NaTPB) or potassium tetraphenylborate (KTPB) for potentiometric determination of gentamicin sulfate were constructed. Our endeavors of lowering the detection limit for gentamicin ion‐selective electrodes were described. The paper focused on gentamicin carbon paste electrodes based on GNS‐RN as electroactive material, o‐nitrophenyloctyl ether (o‐NPOE) as plasticizer and incorporation of MWCNTs and lipophilic anionic additives (NaTPB and KTPB) which lower the detection limit of the electrodes showing best results for determination of gentamicin ion. The characteristics of the electrodes, GNS‐RN+NaTPB+MWCNTs (sensor 1) and GNS‐RN+KTPB+ MWCNTs (sensor 2), were measured, showing favorable features as they provided measurements of the potential with near‐Nernstian slopes of 29.6±0.3 and 29.1±0.3 mV/decade over the concentration range of 1.0×10−6–1.0×10−2 mol L−1 and pH ranges 3.0–8.2 and 3.0–8.0 in short response times (6.5 sec). Importantly, the electrodes had low detection limits of 3.0×10−7and 3.4×10−7 mol L−1 for the two sensors, respectively. The sensors showed high selectivity for gentamicin ion with respect to a large number of interfering species. The electrodes were successfully applied for the potentiometric determination of GNS ions in pure state, pharmaceutical preparations and human urine with high accuracy and precision. The results of this study were compared with some previously published data using other analytical methods.
New Phenolic Compounds from the Roots of Lentil (Lens culinaris)
Authors: Żuchowski Jerzy , Pecio Łukasz , Reszczyńska Emilia , Stochmal Anna
Published: September 2016

While lentil (Lens culinaris) seeds are phytochemically well characterized, very little is known about secondary metabolites from lentil roots. Our research on lentil roots led to isolation of five phenolic compounds and five group B soyasaponins. Their structures were established using NMR spectroscopy and mass spectrometry. Four phenolics have not been hitherto described in the literature: 4‐O‐β‐d‐glucopyranosyl‐2‐methoxybenzoic acid, (αS)‐4,4′‐di‐O‐β‐d‐glucopyranosyl‐α,2′‐dihydroxydihydrochalcone, (αS)‐4′‐O‐β‐d‐glucopyranosyl‐α,2′,4‐trihydroxydihydrochalcone, and keto‐2‐hydroxyglycitein. The DPPH∙ radical‐scavenging activity of the purified phenolic compounds was additionally evaluated.
Design, Synthesis, and Bioassay of Novel Compounds of Isolongifolenone Oxime Derivatives
Authors: Zhang Wu , Wu Aiqun , Xu Haitang , Mo Yuxing , Chen Jie , Shen Liqun
Published: September 2016

A succession of new isolongifolenone oxime derivatives have been designed and synthesized. The structures of these compounds were identified by IR, 1H‐NMR, 13C‐NMR, mass spectra, and elemental analysis. The bioassays of antibacterial, antifungal, and insecticidal activity were carried out. The in vitro antibacterial and antifungal activities were evaluated by the disk diffusion method, and the minimum inhibitory concentration was determined by the microdilution method, while the insecticidal activity was tested by the spraying method or the straw impregnation method. The results of bioassays showed that compound 3f was more active in resisting all the tested bacterial and fungal organisms when compared to the standard drug amoxicillin at the lowest concentration of 31.3 μg/ml. Compound 4, synthesized by Beckmann rearrangement reaction of isolongifone oxime, exerted moderate insecticidal activity against soybean aphid. Furthermore, compound 3m exhibited more activity in killing armyworms than the standard drug flucycloxuron at the concentration of 0.5 mg/l.
Experimental Evidence of Intramolecular CAr–H···O=C Hydrogen Bonds in the Structure of (Diaryl)tetrahydrofuranones Using Spectroscopic Tools
Authors: Semenok Dmitrii V. , Medvedev Jury J. , Avdontceva Margarita S. , Selivanov Stanislav I. , Sieler Joachim , Mereshchenko Andrey S. , Nikolaev Valerij A.
Published: September 2016

The occurrence of bifurcate H‐bonds CAr–H···O=C in the structure of (diaryl)‐tetrahydrofuranones was experimentally demonstrated using different methods and techniques. The consistent increasing spin–spin coupling constants 1J(C,H) of the ortho‐H‐atoms and low‐field shift of vC=O in IR spectra of 2,2‐(diaryl)tetrahydrofuran‐3(2H)‐ones relative to their 5,5‐diaryl counterparts, as well as pronounced dependence of the ortho‐C–H H‐atoms chemical shifts on the temperature and solvent polarity along with X‐ray diffraction analysis data unambiguously point to the existence of weak CAr–H···O=C H‐bonds in these molecules.
Anti‐inflammatory Activity of Two New Indole Alkaloids from the Stems of Nauclea officinalis
Authors: Chen De‐Li , Ma Guo‐Xu , He Min‐Jun , Liu Yang‐Yang , Wang Xiao‐Bing , Yang Xin‐Quan
Published: September 2016

Two new indole alkaloid derivatives (1, 2), together with six known indole alkaloids (3 – 8) were isolated from the 70% EtOH/H2O extract of the stem of Nauclea officinalis. Their structures were determined on the basis of extensive analyses of spectroscopic data (IR, MS, 1D‐ and 2D‐NMR). All the isolates were evaluated for their anti‐inflammatory activities on lipopolysaccharide (LPS)‐induced nitric oxide (NO) production in RAW 264.7, and all the compounds showed significant inhibitory activities with the IC50 values of 0.82, 6.45, 9.75, 1.34, 3.40, 2.69, 1.58, and 1.96 μm, compared to the positive drug control group aminoguanidine with an IC50 value of 1.80 μm, especially compound 1 had the most significant activity.
Total Synthesis of the Proposed Structure of Ardimerin, and Proposal for its Structural Revision
Authors: Nakayama Ryota , Tanzer Eva‐Maria , Kusumi Takenori , Ohmori Ken , Suzuki Keisuke
Published: September 2016

We report the first total synthesis of the proposed structure of ardimerin, which was achieved in 14 steps starting from 2,3,4‐trimethoxybenzoic acid. The key steps include the β‐selective formation of the crucial C‐glycoside linkage and stepwise construction of the strained eight‐membered salicylide core. The synthesis revealed that the proposed structure 1 does not match the natural product. A proposal is made for reassigning the isolated natural product to the already known structure of bergenin. Interesting properties of the synthetic eight‐membered salicylides are documented, including their susceptibility toward nucleophilic ring opening and the bowl chirality.
Iron‐catalyzed C−H Activation
Authors: Su Miaoshen , Li Cheng , Ma Jingjun
Published: September 2016

Transition‐metal‐catalyzed C–H activation and C–C formation have been receiving considerable attention because of their high atom economy and synthesis efficiency. Iron is widely used in catalytic reactions because it has the advantages of abundance, low cost, accessibility, and environmental friendliness. In recent years, research on the Fe‐catalyzed C–H activation of C–C formation has made considerable progress. This paper summarizes latest studies on iron‐catalyzed C–H activation, classifies the catalysts according to the different valence states of iron, and expounds the catalytic mechanism.