bluuebunny/crossref_metadata_2025 huggingface dataset:
Multiobjective constraints for climate model parameter choices: PragmaticPareto fronts in CESM1
Authors: Langenbrunner B. , Neelin J. D.
Published: July 2017

Global climate models (GCMs) are examples of high‐dimensional input‐output systems, where model output is a function of many variables, and an update in model physics commonly improves performance in one objective function (i.e., measure of model performance) at the expense of degrading another. Here concepts from multiobjective optimization in the engineering literature are used to investigate parameter sensitivity and optimization in the face of such trade‐offs. A metamodeling technique called cut high‐dimensional model representation (cut‐HDMR) is leveraged in the context of multiobjective optimization to improve GCM simulation of the tropical Pacific climate, focusing on seasonal precipitation, column water vapor, and skin temperature. An evolutionary algorithm is used to solve for Pareto fronts, which are surfaces in objective function space along which trade‐offs in GCM performance occur. This approach allows the modeler to visualize trade‐offs quickly and identify the physics at play. In some cases, Pareto fronts are small, implying that trade‐offs are minimal, optimal parameter value choices are more straightforward, and the GCM is well‐functioning. In all cases considered here, the control run was found not to be Pareto‐optimal (i.e., not on the front), highlighting an opportunity for model improvement through objectively informed parameter selection. Taylor diagrams illustrate that these improvements occur primarily in field magnitude, not spatial correlation, and they show that specific parameter updates can improve fields fundamental to tropical moist processes—namely precipitation and skin temperature—without significantly impacting others. These results provide an example of how basic elements of multiobjective optimization can facilitate pragmatic GCM tuning processes.
Elevation angle determination for SuperDARN HF radar layouts
Authors: Shepherd S. G.
Published: July 2017

The international scientific radars known as the Super Dual Auroral Radar Network (SuperDARN) are designed to primarily measure plasma convection at ionospheric altitudes over a large region of the Northern and Southern Hemispheres. SuperDARN radars are equipped with a secondary interferometry array that is used to measure the elevation angle (α) of signals. These values of α have been used in relatively few studies; however, they are important for estimating ionospheric quantities and for accurate geolocation of the ionospheric source region of backscattered signals. The majority of SuperDARN radars are constructed with interferometers that are separated from their main array in one or two dimensions, and a relatively straightforward algorithm gives reasonably accurate results. A solution to the more general case, where offsets in all three dimensions are present, is desirable for future designs and necessary for at least one operational radar. Details of such an algorithm are described here and applied to phase measurements from several radars. For radars with interferometers offset only along the radar boresight and vertical directions, small differences of up to ∼1.5° in α are observed and negative values of α, which are deemed unphysical, are no longer produced. For the radar interferometer that is offset in all three dimensions the resulting values of α are consistent with expected behavior. The algorithm presented here provides a technique for accurately determining α from SuperDARN radars with offsets in all three dimensions and significantly reduces constraints placed on the positioning of interferometers for future SuperDARN radars.
Multiple Liquid Manipulations on Patterned Surfaces with Tunable Adhesive Property
Authors: Zhong Qi‐Zhi , Yi Ming‐Han , Du Yong , He Ai , Xu Zhi‐Kang , Wan Ling‐Shu
Published: July 2017

Micro/nanostructured surfaces with designable wettability show great promise in many fields. This paper reports a new strategy for fabricating superhydrophobic surfaces with tunable water adhesion force by combining multiscale surface structures and mussel‐inspired surface chemistry, which can be used for multiple liquid manipulations. Highly ordered porous films prepared by the breath figure method enable convenient construction of surfaces with honeycomb‐patterned or nanosized pincushion‐like structures. Multiple liquid manipulations including no‐loss transportation of water droplets, water collection, programmable movement of water droplets, and chemical reaction monitoring are demonstrated on the micro/nanostructured surfaces. The proposed method is facile, energy‐efficient, and can be conducted for the preparation of superhydrophobic surfaces with high contrast adhesion patterns.
Modulating the Spatial Electrostatic Potential for 1D Colloidal Nanoparticles Assembly
Authors: Chen Jianmei , Huang Jing , Toma Andrea , Zhong Liubiao , Cui Zequn , Shao Weijing , Li Ziyang , Liang Wenkai , De Angelis Francesco , Jiang Lin , Chi Lifeng
Published: July 2017

1D nanoparticle arrangements have gained widespread attention because of their unique collective physical properties and potential applications in functional devices. To push the device integration toward its intrinsic limits, the precise positioning of colloidal nanoparticles into 1D layout is still a challenging task, especially for nanoparticles in the sub‐20 nm range. In this work, a novel strategy based on the synergistic modulation of lateral and bottom electrostatic potential of grooves is applied, thus demonstrating a high‐resolution confinement of 1D colloidal nanoparticle arrays. The mechanism of spatial potential modulation is elucidated in details, through the combination of quantitative theoretical modeling and consistent experimental results. A crystal‐clear guide for the development of novel applications with both fundamental and technological perspectives is therefore provided.
Biallelic COL3A1 mutations result in a clinical spectrum of specific structural brain anomalies and connective tissue abnormalities
Authors: Horn Denise , Siebert Eberhard , Seidel Ulrich , Rost Imma , Mayer Karin , Abou Jamra Rami , Mitter Diana , Kornak Uwe
Published: July 2017

Vascular Ehlers–Danlos syndrome (type IV) is an autosomal dominant disorder caused by heterozygous variants of COL3A1. We identified biallelic COL3A1 variants in two unrelated families. In a 3‐year‐old female with developmental delay the nonsense variant c.1282C>T, p.(Arg428*) was detected in combination the c.2057delC, p.(Pro686Leufs*105) frame shift variant. Both compound heterozygous variants were novel. This patient was born with bilateral clubfoot, joint laxity, and dysmorphic facial features. At the age of 2 years she developed an aneurysmal brain hemorrhage. Cerebral MRI showed a peculiar pattern of profound cerebral abnormalities including bilateral frontoparietal polymicrogyria of the cobblestone variant. In the second family, the two affected siblings were homozygous for the missense variant c.145C<G, p.(Pro49Ala) of COL3A1 and showed cobblestone‐like cortical malformation, cerebellar cysts, and white matter abnormalities, developmental delay, and seizures. To date, three further families have been reported with biallelic variants of this gene and specific structural brain anomalies in all, and a severe Ehlers–Danlos syndrome phenotype in some. Bilateral frontoparietal polymicrogyria of the cobblestone variant, cerebellar microcysts, and abnormalities of the white matter characterize this brain phenotype and resemble neurological manifestations in individuals with autosomal recessive mutations in GPR56, which serves as a ligand of COL3A1. In concordance with the findings in knock out mice, the collagen III protein plays a role in the regulation of cortical development in addition to its well‐known function in connective tissue formation.
MED resulting from recessively inherited mutations in the gene encoding calcium‐activated nucleotidase CANT1
Authors: Balasubramanian Karthika , Li Bing , Krakow Deborah , Nevarez Lisette , Ho Patric J. , Ainsworth Julia A. , Nickerson Deborah A. , Bamshad Michael J. , Immken LaDonna , Lachman Ralph S. , Cohn Daniel H.
Published: July 2017

Multiple Epiphyseal Dysplasia (MED) is a relatively mild skeletal dysplasia characterized by mild short stature, joint pain, and early‐onset osteoarthropathy. Dominantly inherited mutations in COMP, MATN3, COL9A1, COL9A2, and COL9A3, and recessively inherited mutations in SLC26A2, account for the molecular basis of disease in about 80–85% of the cases. In two families with recurrent MED of an unknown molecular basis, we used exome sequencing and candidate gene analysis to identify homozygosity for recessively inherited missense mutations in CANT1, which encodes calcium‐activated nucleotidase 1. The MED phenotype is thus allelic to the more severe Desbuquois dysplasia phenotype and the results identify CANT1 as a second locus for recessively inherited MED.
Whole exome sequencing identified genetic variations in Chinese hemangioblastoma patients
Authors: Ma Dexuan , Yang Jingyun , Wang Ying , Huang Xiang , Du Guhong , Zhou Liangfu
Published: July 2017

Hemangioblastomas (HBs) are uncommon tumors characterized by the presence of inactivating alterations in the von Hippel‐Lindau (VHL) gene in inherited cases and by infrequent somatic mutation in sporadic entities. We performed whole exome sequencing on 11 HB patients to further elucidate the genetics of HBs. A total of 270 somatic variations in 219 genes, of which there were 86 mutations in 67 genes, were found in sporadic HBs, and 184 mutations were found in 154 genes in familial HBs. C: G>T: A and T: A>C: G mutations are relatively common in most HB patients. Genes harboring the most significant mutations include PCDH9, KLHL12, DCAF4L1, and VHL in sporadic HBs, and ZNF814, DLG2, RIMS1, PNN, and MUC7 in familial HBs. The frequency of CNV varied considerably within sporadic HBs but was relatively similar within familial HBs. Five genes, including OTOGL, PLCB4, SCEL, THSD4, and WWOX, have CNVs in the six patients with sporadic HBs, and three genes, including ABCA6, CWC27, and LAMA2, have CNVs in the five patients with familial HBs. We found new genetic mutations and CNVs that might be involved in HBs; these findings highlight the complexity of the tumorigenesis of HBs and pinpoint potential therapeutic targets for the treatment of HBs.
Computational fluid dynamics of a horizontal hydrocyclone for freezing desalination
Authors: Junkratuek A. , Srudhiprom J. , Srinophakun T.
Published: July 2017

Freezing desalination is based on the principle that ice can be nucleated and grown, while excluding impurities. The water is frozen out of aqueous solution and becomes an ice crystal. Horizontal hydrocyclones are compact and simple centrifugal separation devices that have a low pressure drop. They have great potential for separating ice slurry from brine slurry. This work presents an in‐depth study of ice‐brine separation using a horizontal hydrocyclone and computational fluid dynamics. Computational fluid dynamics fluent has been performed with the Reynolds stress model and the Eulerian‐granular approach. The effects of inlet velocity, ice inlet fraction, overflow diameter, and underflow diameter were investigated. The results show that the horizontal hydrocyclone can successfully separate ice from a brine slurry, with a lower solid volume fraction and a high inlet velocity. © 2017 Curtin University and John Wiley & Sons, Ltd.
Discrete‐Time Consensus Filters for Average Tracking of Time‐Varying Inputs on Directed Switching Graphs
Authors: Li Shuai , Guo Yi
Published: July 2017

In this paper, we consider discrete‐time distributed estimation on a directed graph with switching topologies. Motivated by a recent PI consensus filter, we modify the protocol and remove the limitation of undirected graph and gain conditions with requirement for global topological information. The protocol is then extended to switching topologies. Convergence analysis is conducted for constant inputs under both balanced directed and general directed graphs with topological switching. Then, the result is extended to all cases for time‐varying inputs with an analytical derivation of the error bound. Satisfactory simulation results are shown to validate theoretical claims.
Singular Perturbation Method for Smart Building Temperature Control Using Occupant Feedback
Authors: Gupta Santosh K. , Kar Koushik , Mishra Sandipan , Wen John T.
Published: July 2017

In this work we propose a framework for incorporating occupant feedback towards temperature control of multi‐occupant spaces, and analyze it using singular perturbation theory. Such a system would typically have to accommodate occupants with different temperature preferences, and incorporate that with thermal correlation among multiple zones to obtain optimal control for minimization of occupant discomfort and energy cost. In current practice, an acceptable temperature set point for the occupancy level of the zone is estimated, and the control law is designed to maintain temperature at the corresponding set point irrespective of the changes in occupancy and the preferences of multiple occupants. Proposed algorithm incorporates active occupant feedback to minimize aggregate user discomfort and total energy cost. Occupant binary feedback in the form of hot/cold or thermal comfort preference input is used by the control algorithm. The control algorithm also takes the energy cost into account, trading it off optimally with the aggregate occupant discomfort. For convergence to the optimal, sufficient separation between the occupant feedback frequency and the temperature dynamics of system is necessary; in absence of which, the occupant feedback provided do not correctly reflect the effect of current control input value on occupant discomfort. Under sufficient time scale separation, using singular perturbation theory, we establish the stability condition of the system and show convergence of the proposed solution to the desired temperature that minimizes energy cost plus occupant discomfort. The occupants are only assumed to be rational in that they choose their own comfort range to minimize individual thermal discomfort. Optimization for a multi‐zone building also takes into account the thermal correlation among different zones. Simulation study with parameters based on our test facility, and experimental study conducted in the same building demonstrates performance of the algorithm under different occupancy and ambient conditions.
p‐Coumaric acid, a dietary polyphenol ameliorates inflammation and curtails cartilage and bone erosion in the rheumatoid arthritis rat model
Authors: Neog Manoj Kumar , Joshua Pragasam Samuel , Krishnan Moorthy , Rasool Mahaboobkhan
Published: July 2017

This study was designed to explore the underlying mechanism of p‐coumaric acid (CA), a dietary polyphenol in adjuvant‐induced arthritis (AIA) rat model with reference to synovitis and osteoclastogenesis. Celecoxib (COX‐2 selective inhibitor) (5 mg/kg b.wt) was used as a reference drug. CA remarkably suppressed the paw edema, body weight loss and inflammatory cytokine and chemokine levels (TNF‐α, IL‐1β, IL‐6, and MCP‐1) in serum and ankle joint of arthritic rats. Consistently, CA reduced the expression of osteoclastogenic factors (RANKL and TRAP), pro‐inflammatory cytokines (TNF‐α, IL‐1β, IL‐6, and IL‐17), and inflammatory enzymes (iNOS and COX‐2) in arthritic rats. However, OPG expression was found elevated. Besides, the abundance of transcription factors (NF‐κB‐p65, and p‐NF‐κB‐p65, NFATc‐1, and c‐Fos) and MAP kinases (JNK, p‐JNK, and ERK1/2) expression was alleviated in CA administered arthritic rats. In addition, CA truncated osteoclastogenesis by regulating the RANKL/OPG imbalance in arthritic rats and suppressing the RANKL‐induced NFATc‐1 and c‐Fos expression in vitro. Radiological (CT and DEXA scan) and histological assessments authenticated that CA inhibited TRAP, bone destruction and cartilage degradation in association with enhanced bone mineral density. Taken together, our findings suggest that CA demonstrated promising anti‐arthritic effect and could prove useful as an alternative drug in RA therapeutics. © 2017 BioFactors, 43(5):698–717, 2017
MiR‐376a suppresses the proliferation and invasion of non‐small‐cell lung cancer by targeting c‐Myc
Authors: Wang Youyu , Cong Wei , Wu Gang , Ju Xueming , Li Zhixi , Duan Xin , Wang Xueli , Gao Hong
Published: July 2017

It has been reported that miR‐376a is involved in the formation and progression of several types of cancer. However, the expression and function of miR‐376a is still unknown in non‐small cell lung carcinomas (NSCLC). In this study, the expression of miR‐376a in NSCLC tissues and cell lines were examined by real‐time PCR, the effects of miR‐376a on cell proliferation, apoptosis and invasion were evaluated in vitro. Luciferase reporter assay was performed to identify the targets of miR‐376a. The results showed that miR‐376a was significantly downregulated in NSCLC tissues and cell lines. Restoration of miR‐376a in NSCLC cell line A549 significantly inhibited cell proliferation, increased cell apoptosis and suppressed cell invasion, compared with control‐transfected A549 cells. Luciferase reporter assay showed that c‐Myc, an oncogene that regulating cell survival, angiogenesis and metastasis, was a direct target of miR‐376a. Over‐expression of miR‐376a decreased the mRNA and protein levels of c‐Myc in A549 cells. In addition, upregulation of c‐Myc inhibited miR‐376a‐induced inhibition of cell proliferation and invasion in A549 cells. Therefore, our results indicate a tumor suppressor role of miR‐376a in NSCLC by targeting c‐Myc. miR‐376a may be a promising therapeutic target for NSCLC.
Salvage of an osteocutaneous thermonecrosis secondary to tibial reaming by the induced membrane procedure
Authors: Cambon‐Binder Adeline , Revol Marc , Hannouche Didier
Published: July 2017

Key Clinical Message

Osteocutaneous thermonecrosis is a rare but devastating complication of tibial reaming, which can cause large and infected bone and cutaneous defects. The case presented here illustrates that the induced membrane technique described by Masquelet is a valuable option in treating this complication.
Promotional Effect of Fe Impurities in Graphene Precursors on the Activity of MnOX/Graphene Electrocatalysts for the Oxygen Evolution and Oxygen Reduction Reactions
Authors: Morales Dulce M. , Masa Justus , Andronescu Corina , Schuhmann Wolfgang
Published: July 2017

Bifunctional oxygen electrocatalysts were fabricated following a three‐step synthesis method, which consisted of i) liquid‐phase exfoliation of graphite in the presence of nitrogen‐containing manganese macrocyclic complexes, using DMF as the dispersion medium under formation of few‐layer graphene sheets. Subsequently, ii) solvent removal by vacuum filtration and drying, and iii) pyrolysis of the resulting composites under an inert gas atmosphere with subsequent mild calcination yielded manganese oxides embedded within a graphitic carbon matrix (MnOX/G). We further demonstrate that traces of Fe impurities in the used graphite result in enhanced electrocatalytic activity of the MnOX/G towards both the oxygen reduction and the oxygen evolution reactions, owing to synergistic interaction of the iron impurities with the species formed upon thermal decomposition of Mn macrocyclic complexes.
Ferroelectric Fractional‐Order Capacitors
Authors: Agambayev Agamyrat , Patole Shashikant P. , Farhat Mohamed , Elwakil Ahmed , Bagci Hakan , Salama Khaled N.
Published: July 2017

Poly(vinylidene fluoride)‐based polymers and their blends are used to fabricate electrostatic fractional‐order capacitors. This simple but effective method allows us to precisely tune the constant phase angle of the resulting fractional‐order capacitor by changing the blend composition. Additionally, we have derived an empirical relationship between the ratio of the blend constituents and the constant phase angle to facilitate the design of a fractional‐order capacitor with a desired constant phase angle. The structural composition of the fabricated blends is investigated by using Fourier transform infrared spectroscopy and X‐ray diffraction techniques.
Regulated Drug Release Abilities of Calcium Carbonate–Gelatin Hybrid Nanocarriers Fabricated via a Self‐Organizational Process
Authors: Murai Kazuki , Kurumisawa Kazuya , Nomura Yoshihiro , Matsumoto Mutsuyoshi
Published: July 2017

In this study, we investigated the drug‐releasing behavior of a calcium carbonate (CaCO3)–gelatin hybrid nanocarrier, fabricated through a single process using biomimetic mineralization. The organic scaffold (gelatin) of the fabricated nanocarrier is responsible for its capacity to load anionic drugs and for controlling the morphology of the inorganic matrix (CaCO3). We studied the drug‐releasing properties of the nanocarrier by investigating the response of the CaCO3 matrix to acidic conditions. We found that under neutral conditions, drug release from the nanocarrier was inhibited, whereas under acidic conditions, the drug was efficiently released. Therefore, drug release from the nanocarrier is largely dependent on the surrounding pH.
Aquivion Perfluorosulfonic Superacid as an Efficient Pickering Interfacial Catalyst for the Hydrolysis of Triglycerides
Authors: Shi Hui , Fan Zhaoyu , Hong Bing , Pera‐Titus Marc
Published: July 2017

Rational design of the surface properties of heterogeneous catalysts can boost the interfacial activity in biphasic reactions through the generation of Pickering emulsions. This concept, termed Pickering interfacial catalysis (PIC), has shown promising credentials in acid‐catalyzed transesterification, ester hydrolysis, acetalization, etherification, and alkylation reactions. PIC has now been applied to the efficient, solvent‐free hydrolysis of the triglyceride glyceryl trilaurate to lauric acid, catalyzed by Aquivion perfluorosulfonic superacid at mild conditions (100 °C and ambient pressure).
Towards Extending Solar Cell Lifetimes: Addition of a Fluorous Cation to Triple Cation‐Based Perovskite Films
Authors: Salado Manuel , Fernández M. Asunción , Holgado Juan P. , Kazim Samrana , Nazeeruddin Mohammad Khaja , Dyson Paul J. , Ahmad Shahzada
Published: July 2017

Organohalide perovskites have emerged as highly promising replacements for thin‐film solar cells. However, their poor stability under ambient conditions remains problematic, hindering commercial exploitation. The addition of a fluorous‐functionalized imidazolium cation during the preparation of a highly stable cesium‐based mixed perovskite material Cs0.05(MA0.15FA0.85)0.95Pb(I0.85Br0.15)3 (MA=methylammonium; FA=formamidinium) has been shown to influence its stability. The resulting materials, which vary according to the amount of the fluorous‐functionalized imidazolium cation present during fabrication, display a prolonged tolerance to atmospheric humidity (>100 days) along with power conversion efficiencies exceeding 16 %. This work provides a general route that can be implemented in a variety of perovskites and highlights a promising way to increase perovskite solar cell stability.
Carbon Dioxide Capture by Aqueous Ionic Liquid Solutions
Authors: Simon Nathalia M. , Zanatta Marcileia , dos Santos Francisco P. , Corvo Marta C. , Cabrita Eurico J. , Dupont Jairton
Published: July 2017

Confined water in aqueous solutions of imidazolium‐based ionic liquids (ILs) associated with acetate and imidazolate anions react reversibly with CO2 to yield bicarbonate. Three types of CO2 sorption in these “IL aqueous solutions” were observed: physical, CO2‐imidazolium adduct generation, and bicarbonate formation (up to 1.9 molbicarbonate mol−1 of IL), resulting in a 10:1 (molar ratio) total absorption of CO2 relative to imidazolate anions in the presence of water 1:1000 (IL/water). These sorption values are higher than the classical alkanol amines or even alkaline aqueous solutions under similar experimental conditions.
Development and validation of an optical biosensor for rapid monitoring of adalimumab in serum of patients with Crohn's disease
Authors: Bian Sumin , Lu Jiadi , Delport Filip , Vermeire Séverine , Spasic Dragana , Lammertyn Jeroen , Gils Ann
Published: July 2017

Therapeutic drug monitoring of adalimumab is recommended to improve therapeutic outcome in patients with Crohn's disease. Performing an ELISA requires a rather long time‐to‐result and the necessity of collecting multiple samples to decrease the cost per adalimumab determination. In this study, we aim to develop and validate a rapid assay suitable for measuring a single adalimumab serum sample using a fiber‐optic surface plasmon resonance (FO‐SPR) based sensor. Therefore, we have immobilized MA‐ADM28B8 as capture antibody on an FO‐probe and conjugated MA‐ADM40D8 as detecting antibody to gold nanoparticles. A dose–response curve ranging from 2.5 to 40 ng/mL adalimumab was obtained in 1/400 diluted serum. Serum samples of patients with adalimumab concentrations between 1 and 16 μg/mL were measured whereas the negative control, a sample spiked with infliximab at a concentration of 16 μg/mL, showed no significant signal. Using a pre‐functionalized FO‐probe, the technology requires less than 45 minutes for measuring a single sample. Comparison of measurements between the biosensor and the ELISA revealed an excellent agreement with a Pearson r coefficient of 0.99 and an intra‐class coefficient of 0.99. The reduced assay time and the possibility of measuring a single sample are major advantages compared to the ELISA. The developed and validated optical adalimumab biosensor could be a valuable point‐of‐care diagnostic tool for adalimumab quantification in patients with Crohn's disease.
Reproductive consequences of habitat fragmentation for a declining resident bird of the longleaf pine ecosystem
Authors: Winiarski Jason M. , Moorman Christopher E. , Carpenter John P. , Hess George R.
Published: July 2017

Habitat loss and fragmentation are major threats to bird population persistence. Yet, our understanding of the demographic factors behind the adverse effects of fragmentation remains limited for many species. We studied the breeding demographics of the Bachman's Sparrow (Peucaea aestivalis), a species of conservation concern that is associated with highly imperiled longleaf pine ecosystems in the southeastern United States. We quantified the effects of local‐ and landscape‐scale factors on different components of reproductive success (i.e., pairing success and probability of fledging offspring) for 96 male sparrows at eight sites in southeastern North Carolina. Pairing success of monitored sparrows was 69%, and 77% of paired males fledged ≥1 offspring. Habitat amount in the surrounding landscape, rather than local habitat quality, was the most influential predictor of pairing success for male Bachman's Sparrows. In contrast, we documented no predictors of successfully fledging offspring for paired males. We infer that reduced pairing success is limiting reproduction in isolated landscapes and may be a contributing factor for the low occupancy and declines of Bachman's Sparrow in our study region. Overall, our results suggest that managers can promote breeding opportunities for Bachman's Sparrows by prioritizing resources to patches near large, preexisting longleaf pine forest to ensure ≥20% habitat within the surrounding landscape.
Influence of Base Strength on the Proton‐Transfer Reaction by Density Functional Theory
Authors: Yuan Binfang , He Rongxing , Shen Wei , Li Ming
Published: July 2017

DFT methods have been used to investigate base‐assisted effects on proton‐transfer reactions, including the cleavage of C–H bonds in metal‐catalyzed organic synthesis. Anion ligands (OTf–, BF4–, or SbF6–) have been shown to effectively promote cleavage of the C–H bond and then assist proton migration as a proton‐transfer shuttle. Importantly, the calculations revealed that the catalytic activity (OTf– > BF4– > SbF6–) in the C–H bond‐breaking step is controlled by the Brønsted/Lewis basicity of the anion ligand (OTf– > BF4– > SbF6–) through a hydrogen‐bonding (base···C–H) interaction. Additives play a similar role to the anion ligands, and the use of a strong base as an additive is much more effective in promoting cleavage of the C–H bond than a weak base. In short, the present study has provided a greater understanding of the effects of base strength on proton‐transfer reactions involving C–H bond cleavage and offers guidance for the future design of new catalysts and new reactions.
Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction
Authors: Ramakrishna Kankanala , Sivasankar Chinnappan
Published: July 2017

We report a method to produce amido esters and amido phosphonates. Octacarbonyldicobalt [Co2(CO)8] was found to be an efficient nongaseous CO source that could be used as a reagent for the carbonylation of diazo esters and diazo phosphonates under mild reaction conditions. A number of diazo esters and diazo phosphonates smoothly underwent the reaction with CO, which was generated from Co2(CO)8, to produce the corresponding ketenes. The subsequent reaction with an amine afforded the expected amido esters and phosphonates. By applying the developed protocol, we synthesized a number of amido esters and amido phosphonates. Characterization of these compounds was achieved by using standard spectroscopic and analytical techniques as well as crystal structure analysis for four of the products.
Marginally Hydrogenated Triphasic Titania Nanotubes for Effective Visible‐Light Photocatalytic Hydrogen Generation
Authors: Preethi Laguduva K. , Mathews Tom , Walczak Lukasz , Gopinath Chinnakonda S.
Published: July 2017

We report the first demonstration of hydrogen‐annealed triphase TiO2 nanotubes (anatase–rutile–brookite) (T‐ARB) as a visible‐light‐active photocatalyst for water splitting with high quantum efficiency. As‐synthesized T‐ARB was annealed under hydrogen atmosphere at 250 and 450 °C for 2 h. We found that the tubular structures were retained in the hydrogenated TiO2 samples. It was observed that the concentrations of Ti3+ and the oxygen vacancies and their distribution significantly increased with respect to the hydrogen annealing temperature. Such changes in defects were found to be critical in enhancing the photocatalytic activity of the hydrogen‐annealed triphase TiO2 nanotubes. The triphase TiO2 nanotubes hydrogen annealed at 450 °C were 16 times more efficient than pristine TiO2. Such an increase in the photocatalytic activity was explained by a triphase band diagram with defect states below the conduction band of each phase, which facilitated visible‐light activity and easy transfer of charge carriers from one phase to another. Our study showed that the well‐designed multiphase construction with oxygen vacancies enhanced the photocatalytic activity tremendously owing to the presence of a higher number of phase junctions.
Hydrogen Generation on Metal/Mesoporous Oxides: The Effects of Hierarchical Structure, Doping, and Co‐catalysts
Authors: Moon Song Yi , Gwag Eun Heui , Park Jeong Young
Published: July 2017

Photocatalytic water splitting for the generation of hydrogen fuel under solar‐light illumination is a sustainable and renewable energy technology to solve environmental issues. Numerous attempts have been made to develop a stable and efficient visible‐light‐driven photocatalyst for hydrogen evolution. Several factors (e.g., morphology, surface area, crystallinity, and band structure of the catalyst and charge transfer at the oxide‐metal interface) have been shown to affect the solar‐to‐hydrogen energy‐conversion efficiency. Recently, various modification strategies for metal‐oxide photocatalysts, including cation/anion doping for visible‐light harvesting, have been suggested. Furthermore, a series of new engineering methods that introduce co‐catalysts, dye sensitizers, and quantum dots appear to improve the photocatalytic activity for hydrogen generation. In this article, we give an overview of the molecular‐scale factors that influence the efficiency of hydrogen evolution and outline recent progress of commonly used engineering strategies that search for higher efficiency in the generation of hydrogen. Specifically, nanostructured photocatalysts, including hierarchical mesoporous structures, were investigated for the production of hydrogen. Finally, great achievements in the emerging field of surface‐plasmon‐induced hot‐electron‐driven hydrogen generation are discussed.
Structured identification of response options to address environmental health risks at the Agbogbloshie electronic waste site
Authors: Cazabon Danielle , Fobil Julius N , Essegbey George , Basu Niladri
Published: July 2017

Electronic waste (e-waste) is a growing problem across low- and middle-income countries. Agbogbloshie (Accra, Ghana) is among the world's largest and most notorious e-waste sites, with an increasing number of studies documenting a range of environmental health risks. The present study aimed to provide national, regional, and international stakeholders with a summary of expert opinion on the most pressing problems arising from e-waste activities at Agbogbloshie, as well as suggested solutions to address these problems. Structured interviews were performed between April and September 2015 that used a Logical Framework Approach as a scoping exercise to gauge problems and benefits of e-waste recycling, and the Delphi methodology to identify response options. Stakeholders (n = 19) from 15 institutions were interviewed with 2 rounds of a Delphi Poll: open-ended interviews followed by an electronic questionnaire in which experts ranked various proposed response options based on health, environmental, social, and economic benefit and feasibility. The goal was to prioritize potential interventions that would address identified problems at Agbogbloshie. Experts identified the most beneficial and feasible options in decreasing rank order as follows and prefaced by the statement “it is recommended that”: 1) there be further research on the health effects; 2) e-waste workers be given appropriate personal protective equipment; 3) the Ministry of the Environment, Science, Technology and Innovation re-visit Ghana's Hazardous Waste Bill; 4) e-waste workers be involved in the planning process of interventions and are be kept informed of any results; and 5) there be increased education and sensitization on hazards related to e-waste for both workers and the general public. These solutions are discussed in relation to ongoing dialogue at the international level concerning e-waste recycling interventions, with strengths and weaknesses examined for the Ghanaian context. Integr Environ Assess Manag 2017;13:980–991. ©2017 SETAC

Key Points

This is one of the first studies to systematically identify options to address the environmental health concerns associated with e-waste, even though the activity is escalating worldwide. Key response options included a need for more research, the use of personal protective equipment, passing national laws, involvement of the workers themselves in the planning of interventions, and education. The outcome of the study has direct and immediate relevance to a number of active discussions at the national, regional, and international levels concerning the assessment and management of e-waste.
In vivo comparison of jellyfish and bovine collagen sponges as prototype medical devices
Authors: Widdowson Jonathan P. , Picton Alex J. , Vince Valerie , Wright Chris J. , Mearns‐Spragg Andrew
Published: July 2017

Jellyfish have emerged as a source of next generation collagen that is an attractive alternative to existing sources, such as bovine and porcine, due to a plentiful supply and providing a safer source through lack of bovine spongiform encephalopathy (BSE) transmission risk and potential viral vectors, both of which could be transmitted to humans. Here we compare collagen implantable sponges derived for the first time from the Rhizostoma pulmo jellyfish. A further novelty for the research was that there was a comparison for sponges that were either uncrosslinked or crosslinked using 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide hydrochloride (EDC), and an assessment on how this affected resorption, as well as their biocompatibility compared to bovine type I collagen sponges. The scaffolds were prepared and examined using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE) and scanning electron microscopy (SEM). The samples were implanted in adult male Wistar rats for in vivo experimentation. Both crosslinked and uncrosslinked jellyfish collagen sponges showed a significant reduction in histopathology scores over the course of the study, whereas the bovine collagen sponge scores were not significantly reduced. Both jellyfish collagen sponges and the bovine sponge were tolerated well by the hosts, and a recovery was visible in all samples, suggesting that R. pulmo jellyfish‐derived collagen could offer compelling biocompatibility with wound healing applications. We also demonstrate that noncrosslinked samples could be safer with better resorption times than crosslinked samples. © 2017 The Authors Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1524–1533, 2018.
A Review of Moxifloxacin for the Treatment of Drug‐Susceptible Tuberculosis
Authors: Naidoo Anushka , Naidoo Kogieleum , McIlleron Helen , Essack Sabiha , Padayatchi Nesri
Published: July 2017

Moxifloxacin, an 8‐methoxy quinolone, is an important drug in the treatment of multidrug‐resistant tuberculosis and is being investigated in novel drug regimens with pretomanid, bedaquiline, and pyrazinamide, or rifapentine, for the treatment of drug‐susceptible tuberculosis. Early results of these studies are promising. Although current evidence does not support the use of moxifloxacin in treatment‐shortening regimens for drug‐susceptible tuberculosis, it may be recommended in patients unable to tolerate standard first‐line drug regimens or for isoniazid monoresistance. Evidence suggests that the standard 400‐mg dose of moxifloxacin used in the treatment of tuberculosis may be suboptimal in some patients, leading to worse tuberculosis treatment outcomes and emergence of drug resistance. Furthermore, a drug interaction with the rifamycins results in up to 31% reduced plasma concentrations of moxifloxacin when these are combined for treatment of drug‐susceptible tuberculosis, although the clinical relevance of this interaction is unclear. Moxifloxacin exhibits extensive interindividual pharmacokinetic variability. Higher doses of moxifloxacin may be needed to achieve drug exposures required for improved clinical outcomes. Further study is, however, needed to determine the safety of proposed higher doses and clinically validated targets for drug exposure to moxifloxacin associated with improved tuberculosis treatment outcomes. We discuss in this review the evidence for the use of moxifloxacin in drug‐susceptible tuberculosis and explore the role of moxifloxacin pharmacokinetics, pharmacodynamics, and drug interactions with rifamycins, on tuberculosis treatment outcomes when used in first‐line tuberculosis drug regimens.
Single‐layered retardation films with negative wavelength dispersion birefringence made from liquid‐crystalline monomers
Authors: Yamamoto Mika , Endo Koichi , Kuwana Yasuhiro , Nishiyama Isa
Published: July 2017

Organic light‐emitting diode displays have a cathode composed of a layer of highly reflective metal. Reflection of external light from this layer can be suppressed with a broadband quarter‐wave plate. Although various types of quarter‐wave plate retardation films have been prepared by copolymerizing, mixing, or laminating multiple polymers, ideal wavelength dispersion has not been achieved with thin retardation films because of their relatively low birefringence and the complexity of the procedure required manufacturing them. In this study, we developed (i) new liquid‐crystalline monomers with negative wavelength dispersion birefringence that we used to obtain thin, single‐layered retardation films suitable for coating and (ii) retardation films with different molecular alignments. We found that the monomers showed high solubility and high regularity of molecular alignment, with less damage to the substrate and alignment films. We also investigated the wavelength dispersion and thermal stability of the films. We succeeded in developing retardation films that had a homeotropic alignment or a hybrid alignment with negative wavelength dispersion. These alignments can be used to obtain antireflection films with an improved viewing angle for organic light‐emitting diode displays or next‐generation thin displays.
Pharmacologic Considerations in the Management of Patients Receiving Left Ventricular Percutaneous Mechanical Circulatory Support
Authors: Allender J. Erin , Reed Brent N. , Foster Jenna L. , Moretz Jeremy D. , Oliphant Carrie S. , Jennings Douglas L. , DiDomenico Robert J. , Coons James C.
Published: July 2017

Percutaneous mechanical circulatory support (MCS) devices, including the intraaortic balloon pump, Impella, and TandemHeart, are often used for hemodynamic support in the setting of refractory cardiogenic shock. The thrombotic and bleeding complications associated with these devices is well recognized, and the Impella and TandemHeart devices have unique anticoagulation considerations that may influence patient outcomes. Both devices typically require use of a heparinized purge solution in combination with intravenous unfractionated heparin, thereby providing multiple sources of heparin exposure. Each device also has specific monitoring requirements and goal ranges. This review provides an overview of percutaneous MCS devices commonly used in the acute management of left ventricular failure, with an emphasis on pharmacologic considerations. We review recent evidence and guidelines and provide recommendations for appropriate use of anticoagulation during device support. Approaches to managing heparinized purge solutions, monitoring, and the utility of nonheparin anticoagulants are also provided because high‐quality evidence in the literature is limited.
Photodynamic Therapy of Human Hepatoma Using Semiconductor Quantum Dots as Sole Photosensitizer
Authors: Sun Jiaojiao , Guo Yuming , Zhu Lin , Yang Lin , Shi Weike , Wang Kui , Zhang Hua
Published: July 2017

Currently, the studies about photodynamic therapy (PDT) of human cancers have made considerable progress and attracted tremendous attention. The existing photosensitizers used for PDT are mainly organic compounds. In order to enhance their photosensitizing efficacy, some studies reported hybrid photosensitizers consisting of inorganic quantum dots (QDs) and organic photosensitizers. Herein, a new type of photosensitizer consisting of sole semiconductor CdTe QDs with good photosensitizing efficacy, excellent water dispersibility, and stability is reported. The photosensitizer is prepared through a facile one‐step strategy using sodium hyaluronate as a stabilizing and targeting agent. Different from most of the previous reports, the as‐prepared QDs do not show inhibition effects on normal cells in the experimental concentration range, but can also be directly utilized as a photosensitizer to specifically and remarkably inhibit the proliferation of human hepatoma cells. Mechanism studies reveal that the QDs could be specifically internalized by hepatoma cells, considerably induce the generation of intracellular reactive oxidative species under light illumination, and significantly induce the necrosis of hepatoma cells. This work provides an inspiration for the direct application of QDs as a new type of photosensitizer to specifically and significantly treat human hepatoma through PDT.
A Novel Base‐Solvent Controlled Chemoselective Azide Attack on an Ester Group versus Keto in Alkyl 3‐Substituted 3‐Oxopropanoates: Mechanistic Insights
Authors: Pokhodylo Nazariy T. , Shyyka Olga Ya. , Matiychuk Vasyl S. , Obushak Mykola D. , Pavlyuk Volodymyr V.
Published: July 2017

During the exploration of arylazides reactions with alkyl 3‐substituted‐3‐oxopropanoates under the Dimroth reaction conditions (MeONa‐MeOH) azide attack on ester group versus keto was found out in few examples yielding stable 3‐alkyl‐2‐diazo‐3‐oxo‐N‐(aryl)propanamides instead of obvious target 1‐aryl‐5‐alkyl‐1H‐1,2,3‐triazole‐4‐carboxylic acids. The formation of diazocompounds was observed in case of 3‐(4,4‐diethoxymethyl)‐, isopropyl‐, cyclopropyl‐3‐oxopropanoate in the reaction with arylazides, especially, those containing electro‐withdrawing substituents. Influence of the base‐solvent system on diazo products yields was investigated and mechanistic insights of Dimroth reaction were discussed.
Bioinspired Green and Facile Fabrication of Au@Ag@AgCl Hybrid Nanoparticles and Their Catalytic and Antimicrobial Properties
Authors: Devi Thengujam Babita , Ahmaruzzaman Mohammed
Published: July 2017

We describe a novel green synthesis of Au@Ag@AgCl nanoparticles (NPs) using Aquilaria agallocha leaf juice. It was observed that the growths of nanoparticles are ceased within 20 min of reaction time. The results confirmed that the Aquilaria agallocha is a very good eco‐friendly and nontoxic source for the synthesis of nanoparticles as compared to the conventional chemical and physical methods. To the best knowledge of the authors, it was for the first time we developed Au@Ag@AgCl nanoparticles using Aquilaria agallocha leaf juice. The presence of chloride ion in the leaf juice was detected by the Mohr's method. Further it was confirmed by XRD and XPS technique. The synthesized NPs were characterized by several instrumental techniques and spherical in shape with particle size in range of 10–15 nm. Because of the medicinal properties of Aquilaria agallocha leaf juice, synthesized NPs exhibited antimicrobial activity against various pathogens. In this article, we found that the Au@Ag@AgCl NPs showed better antimicrobial properties as compared to the metallic nanoparticles like AgNPs or AuNPs. We also investigated the catalytic property of the synthesized NPs in the reduction of toxic nitrocompounds.
Promoting Effects of Lanthan on Ru/AC for Ammonia Synthesis: Tuning Catalytic Efficiency and Stability Simultaneously
Authors: Ni Jun , Lin Jingdong , Wang Xiuyun , Lin Bingyu , Lin Jianxin , Jiang Lilong
Published: July 2017

La−Ba‐K−Ru/AC catalysts for ammonia synthesis were prepared by co‐impregnation method using graphited active‐carbon as the support and water‐soluble chloride‐free Ru complex as the precursor. The results demonstrate that the La promoted Ba‐K−Ru/AC catalysts exhibit good catalytic activity, high thermal stability and strong resistance against methanation. TEM (Transmission Electron Microscope) and CO (carbon monoxide) chemisorption analysis indicate that the Ru particles had a relatively uniform size of 3∼5 nm and the particle surface might be partially covered by LaOx and BaOx. H2‐TPR (Temperature Programmed Reduction) results suggest that strong interactions might exist between the Ru particles and the promoters (La and Ba). The N2‐TPD (Temperature Programmed Desorption) and H2‐TPD measurements show that the presence of small amount of La enhances the adsorption of N2 and inhibits the adsorption of H2, resulting in higher TOF values and better catalytic performances. Moreover, no obvious agglomeration of Ru particles was observed on the catalysts after heat resistance. The superior catalytic stability of La−Ba‐K−Ru/AC is associated with its strong resistance against methanation of active‐carbon due to highly coverage of ruthenium surface and strong inhibition of hydrogen by promoters.