bluuebunny/crossref_metadata_2025 huggingface dataset:
Heptanuclear Disk‐Like MII3LnIII4 (M = Ni, Co) Coordination Clusters: Synthesis, Structures and Magnetic Properties
Authors: Griffiths Kieran , Harding Chris , Dokorou Vasiliki N. , Loukopoulos Edward , Sampani Stavroula I. , Abdul‐Sada Alaa , Tizzard Graham J. , Coles Simon J. , Lorusso Giulia , Evangelisti Marco , Escuer Albert , Kostakis George E.
Published: July 2017

The synthesis, characterization, crystal structures and magnetic properties of isoskeletal heptanuclear disk‐like MII3LnIII4 coordination clusters with the general formula [CoII3LnIII4(µ3‐OH)6L6(CF3SO3)][(CF3SO3)5] where Ln = Gd (2), Y (3) and [NiII3LnIII4(µ3‐OH)6L6(CF3SO3)][(CF3SO3)5] where Ln = Dy (4), Gd (5), Y (6) are presented. All the compounds are stable in solution as confirmed by ESI‐MS. Magnetic studies were performed for compounds 2, 4, 5 and 6 and indicate ferromagnetic coupling while the magnetocaloric properties of 5 are characterized by ΔSm = –15.4 J kg–1 K–1 at T = 5.0 K and ΔTad = 5.9 K at T = 2.3 K, for µ0ΔH = 7 T.
Recent Advances in Radical Dioxygenation of Olefins
Authors: Bag Raghunath , De Pinaki Bhusan , Pradhan Sourav , Punniyamurthy Tharmalingam
Published: July 2017

Dioxygenation of olefins is a valuable synthetic tool for the construction of 1,2‐diols and α‐oxygenated ketones. The use of radical approaches to achieve this direct 1,2‐difunctionalization has recently made considerable progress. The metal‐catalyzed reactions employ molecular oxygen and air as the oxidants, whereas metal‐free dioxygenation utilizes oxygen and peroxides. These oxidations are effective under mild conditions, with activated olefins found to be the most successful substrates. This microreview covers the recent developments in the radical dioxygenation of olefins, with respect to substrate scope, mechanism, and the advantages and disadvantages of the methods.
Optical Effect of Varying Acceptors in Pyrene Donor–Acceptor–Donor Chromophores
Authors: Keller Samantha N. , Bromby Ashley D. , Sutherland Todd C.
Published: July 2017

Three donor–acceptor–donor (D–A–D) pyrene chromophores are described and compared by DFT computations. The two properties of low energy photon absorption and low energy electrochemical reduction are demonstrated through a pyrene framework. Altering the electron‐acceptor strength of the pyrene core by chemical oxidation or installation of a thiadiazole dioxide heterocycle results in the formation of D–A–D chromophores with absorption bands up to 900 nm and LUMO energy levels of approximately –4.1 eV vs. vacuum.
Far‐Red‐Emitting TEG‐Substituted Squaraine Dye: Synthesis, Optical Properties, and Selective Detection of Cyanide in Aqueous Solution
Authors: Liu Taihong , Liu Xinglei , Valencia Maira A. , Sui Binglin , Zhang Yuanwei , Belfield Kevin D.
Published: July 2017

A comprehensive study of the photophysical properties of triethylene glycol monomethyl ether (TEG)‐substituted squaraine dye SQ1 is presented. SQ1 exhibits strong absorption and intense fluorescence emission in the far‐red spectral region and high photostability. Interestingly, bis‐tegylated SQ1 was characterized to exhibit properties different from its tetrahydroxy analog (SQ2), to which we ascribe attenuation of intermolecular interactions as a result of steric hindrance through introduction of two TEG chains adjacent to the squaraine core. The photophysical properties of SQ1 were also investigated as a function of temperature and pH. In cetyltrimethylammonium bromide (CTAB) micellar media (1.0 mm), the fluorescence quantum yield of SQ1 increased dramatically to 0.22, compared with 0.02 in water. Based on this discovery, SQ1 was found to display excellent sensitivity and selectivity to the presence of cyanide ions (CN–), with a limit of detection of 1.7 µm. The hypothesized CN– sensing mechanism was probed, and visual test strips were developed. This work broadens the family of squaraine dyes and demonstrates SQ1 for use as a fluorescent or visual sensing probe.
Donor–Acceptor Iptycenes with Thermally Activated Delayed Fluorescence
Authors: Voll Constantin‐Christian A. , Engelhart Jens U. , Einzinger Markus , Baldo Marc A. , Swager Timothy M.
Published: July 2017

A new donor–acceptor iptycene containing carbazole donors and a thiadiazoloquinoxaline acceptor was synthesized and its photo‐ and electrochemical properties evaluated. The key intermediate 1 allows a lateral modification through cross‐coupling, and the (triisopropylsilyl)acetylene product 2 exhibits bright yellow fluorescence with emission lifetimes of 2.42 µs in deoxygenated hexane. The long lifetime and high quantum efficiency (73 %) is quenched by O2 and therefore attributed to thermally activated delayed fluorescence (TADF). This approach allows functionalization through cross‐coupling reactions and depicts a promising scaffold for the synthesis of TADF‐active molecules.
A Highly Enantioselective Alkene Methoxycarbonylation Enables a Concise Synthesis of (S)‐Flurbiprofen
Authors: Harkness Gavin J. , Clarke Matthew L.
Published: July 2017

A highly enantioselective synthesis of (S)‐flurbiprofen methyl ester in two steps from commercially available 4‐bromo‐2‐fluoro‐1,1′‐biphenyl is shown. [PdCl2((S)‐xylyl‐phanephos)] catalyst is used to accomplish both Grignard cross‐coupling and the highly enantioselective intermolecular methoxycarbonylation reaction.
Zinc‐Mediated Efficient and Selective Reduction of Carbonyl Compounds
Authors: Mandal Tirtha , Jana Snehasish , Dash Jyotirmayee
Published: July 2017

We herein describe for the first time that an optimized combination of Zn and NH4Cl can be used for the selective reduction of aldehydes and ketones to the corresponding alcohols. The aldehyde and keto groups are selectively reduced in the presence of azide, cyano, epoxy, ester, and carbon–carbon double‐bond functional groups. A broad functional‐group compatibility, chemoselective reduction of aldehydes in the presence of ketones, and selective reduction of isatins at the C3 carbonyl group are the highlights of the present method.
Sensitive and Green Method for Determination of Chemical Oxygen Demand Using a Nano‐copper Based Electrochemical Sensor
Authors: Badr Ibrahim H. A. , Hassan Hamdy H. , Hamed E. , Abdel‐Aziz Ali M.
Published: July 2017

Copper nanoparticles (nano‐Cu) were electrodeposited on the surface of glassy carbon electrode (GCE) potentiostatically at −0.6 V vs. Ag/AgCl for 60 s. The developed nano‐copper modified glassy carbon electrode (nano‐Cu/GCE) was optimized and utilized for electrochemical assay of chemical oxygen demand (COD) using glycine as a standard. The surface morphology and chemical composition of nano‐Cu/GCE were investigated using scanning electron microscope (SEM) and energy dispersive X‐ray spectrometer (EDX), respectively. The electrochemical behavior was investigated using linear sweep voltammetry (LSV) which is characterized by a remarkable anodic peak at ∼0.6 V, compared to bare GCE. This indicates that nano‐Cu enhances significantly the electrochemical oxidation of glycine. The effect of different deposition parameters, such as Cu2+ concentration, deposition potential, deposition time, pH, and scan rate on the response of the developed sensor were investigated. The optimized nano‐Cu/GCE based COD sensor exhibited a linear range of 15 to 629.3 ppm, and a lower limit of detection (LOD) of 1.7 ppm (S/N=3). This developed method exhibited high tolerance level to chloride ion (0.35 M chloride ion has minimal influence). The analytical utility of the prepared COD sensor was demonstrated by investigating the COD recovery (99.8±4.3) and the assay of COD in different water samples. The results obtained were verified using the standard dichromate method.
Derivatization agents for electrochemical detection in amino acid, peptide and protein separations: The hidden electrochemistry?
Authors: Sierra Tania , Crevillen Agustin G. , Escarpa Alberto
Published: July 2017

In proteomics and clinical analysis, LIF and MS are the most used detectors coupled to separation techniques. MS offers good sensitivity and analyte identification ability but, as counterbalance, it is expensive and it needed background electrolytes compatible with mass spectrometers. LIF detection offers the highest sensitivity but, in general, proteins, peptides and amino acids are not fluorescents so it is necessary the use of fluorescence tags. This fact hindered the potential sensitivity of LIF detection due to the difficulty of labeling analytes at extremely low concentrations. In the context of micro‐ and nanofluidics, electrochemical detection (ED) is an excellent alternative to LIF and MS because it offers several advantages such as easy miniaturization, simpler methods, lower cost and high sensitivity in spite of decreasing the electrode size and sample volume. Among ED techniques, amperometric detection (AD and PAD) are the most used. The problem is that the sensitivity is not enough for the majority of proteomics and clinical applications. To overcome this handicap, electrochemical derivatization reagents have been employed with excellent results allowing limits of detection in nanomolar range. This review surveys all papers related to electrochemical derivatization reagents employed for amino acids, peptides and proteins in separation techniques. Additionally, we highlight the possibilities of this electrochemical tags in the context of micro‐ and nano‐ separation techniques and showed potential electrochemical tags which could be employed in the near future for proteomics applications.
CCR: Cost‐aware cell relocation in 6TiSCH networks
Authors: Chang Tengfei , Watteyne Thomas , Vilajosana Xavier , Wang Qin
Published: July 2017

The Internet Engineering Task Force 6TiSCH Working Group standardizes the protocol stack for the Industrial Internet of Things, which combines the industrial performance of IEEE802.15.4 time‐slotted channel hopping (TSCH) with the addressability and Internet integration capabilities of Internet Protocol version 6. The 6top Protocol, which is part of 6TiSCH, allows distributed management of the TSCH communication schedule. The Scheduling Function Zero (SF0) is the default algorithm for a node to decide when to add/remove cells to its neighbors. SF0 picks the cells to add randomly; hence, it is possible that 2 nearby pairs of nodes pick the same cell, resulting in a schedule collision. This article introduces cost‐aware cell relocation (CCR), which is a solution to detect and fix such schedule collisions in a distributed manner. CCR monitors the performance of individual cells and uses that information to detect collisions. When such a collision is detected on a cell, neighbor nodes communicate to relocate that cell to a different slot/channel in the TSCH schedule. We implement CCR and run it on a 5‐node network on the Internet of Things Laboratory testbed. The results show that, compared with today's SF0 and for the same traffic requirements, CCR increases the average packet delivery ratio by 2% and reduces the number of cells that need to be scheduled by 27.3%.
Electrochemical Properties of Niobium Modified AISI316L Stainless Steel Bipolar Plates for Direct Formic Acid Fuel Cell
Authors: Cui Y. F. , Cui J. L. , Xu X. , Cheng F. P. , Wang L. X. , Li S. , Ji S. J. , Sun J. C.
Published: July 2017

To ameliorate the corrosion resistance and surface electrical conductivity of AISI316L stainless steel (316L SS) as bipolar plates for direct formic acid fuel cell (DFAFC), a niobium diffusion layer has been successfully prepared on 316L SS substrate via the plasma surface diffusion alloying (PSDA) technique. The niobium modified AISI316L stainless steel (Nb‐316L SS) has a compact and successive niobium diffusion layer with a lower interfacial contact resistance (ICR) compared with bare 316L SS. The electrochemical behaviors of Nb‐316L SS in simulated varied anode (0.05M H2SO4 + 2 ppm HF + xM formic acid (x = 2, 5, 10 and 15) solution at 50 °C) and cathode (0.05M H2SO4 + 2 ppm HF solution at 50 °C, bubbled with air) DFAFC environments are systematically studied. The results show that the corrosion resistance of 316L SS is distinctly bettered in both anode and cathode environments of DFAFC after the PSDA modification. After 4 h potentiostatic polarization tests, the ICR of bare and Nb‐316L SS have increased at the clamping force of 140 N cm−2, but the increasing amplitude of the ICR for Nb‐316L SS is much smaller than that of bare 316L SS.
Cytokine Mixtures Mimicking Secretomes From Mesenchymal Stem Cells Improve Medication‐Related Osteonecrosis of the Jaw in a Rat Model
Authors: Ogata Kenichi , Matsumura Mayu , Moriyama Masafumi , Katagiri Wataru , Hibi Hideharu , Nakamura Seiji
Published: July 2017

Recently, several studies have demonstrated that intravenous administration of mesenchymal stem cells (MSCs) improve medication‐related osteonecrosis of the jaw (MRONJ), and paracrine effects of secretomes from MSCs have been hypothesized as the primary contributors. These secretomes in conditioned media from human MSCs (MSC‐CM) were previously demonstrated to promote bone and tissue regeneration. Because MSC‐CM contain cytokines monocyte chemoattractant protein (MCP)‐1, insulin growth factor (IGF)‐1, and vascular endothelial growth factor (VEGF) at relatively higher concentrations than other factors, these cytokines were considered as relevant active factors for tissue regeneration. By mixing the recombinant proteins of MCP‐1, IGF‐1, and VEGF, included at the same concentrations in MSC‐CM, we prepared cytokine mixtures mimicking MSC‐CM and then evaluated its therapeutic effects in a rat MRONJ model. In vitro, cytokine mixtures promoted osteogenic differentiation, migration, and proliferation of rat MSCs. In addition, these maintained osteoclastic function. In vivo, we used a rat MRONJ model to examine therapeutic effects of the cytokine mixtures through intravenous administration. In MSC‐CM or cytokine mixture group, open alveolar sockets in 66% or 67% of the rats with MRONJ, respectively, healed with complete soft tissue coverage and socket bones, whereas in the other groups, the exposed necrotic bone with inflamed soft tissue remained. Histological analysis revealed new bone formation and the appearance of osteoclasts in MSC‐CM or cytokine mixture group; however, osteoclasts were significantly reduced in the other groups. Thus, we concluded that intravenous administration of cytokine mixtures might be an effective therapeutic modality for treating patients with MRONJ. © 2017 The Authors JBMR Plus published by Wiley Periodicals, Inc. on behalf of American Society for Bone and Mineral Research
MALDI‐FT‐ICR‐MS for archaeological lipid residue analysis
Authors: Oras Ester , Vahur Signe , Isaksson Sven , Kaljurand Ivari , Leito Ivo
Published: July 2017

Soft‐ionization methods are currently at the forefront of developing novel methods for analysing degraded archaeological organic residues. Here, we present little‐used soft ionization method of matrix assisted laser desorption/ionization‐Fourier transform‐ion cyclotron resonance‐mass spectrometry (MALDI‐FT‐ICR‐MS) for the identification of archaeological lipid residues. It is a high‐resolution and sensitive method with low limits of detection capable of identifying lipid compounds in small concentrations, thus providing a highly potential new technique for the analysis of degraded lipid components. A thorough methodology development for analysing cooked and degraded food remains from ceramic vessels was carried out, and the most efficient sample preparation protocol is described. The identified components, also controlled by independent parallel analysis by gas chromatography‐mass spectrometry (GC‐MS) and gas chromatography‐combustion‐isotope ratio mass spectrometry (GC‐C‐IRMS), demonstrate its capability of identifying very different food residues including dairy, adipose fats as well as lipids of aquatic origin. The results obtained from experimentally cooked and original archaeological samples prove the suitability of MALDI‐FT‐ICR‐MS for analysing archaeological organic residues. Sample preparation protocol and identification of compounds provide future reference for analysing various aged and degraded lipid residues in different organic and mineral matrices.
Simulations of the observed ‘jump’ in the West African monsoon and its underlying dynamics using the MIT regional climate model
Authors: Im Eun‐Soon , Eltahir Elfatih A. B.
Published: July 2017

The observed seasonal migration of rainfall associated with the West African monsoon (WAM) is characterized by two regimes of relatively intense rainfall: an early, intense peak over the Guinean Coast during late May to early July; and a late, less‐intense peak over the Sahel during mid‐July to mid‐September. The transition between these two rainfall regimes occurs relatively quickly around the beginning of July. This quick transition can be described as a ‘jump’ of the WAM into the continent. Eltahir and Gong (1996) proposed a theory for the WAM whereby the solar radiation forcing during the summer shapes a distribution of boundary‐layer entropy that peaks over the continent. By assuming a quasi‐equilibrium balance between moist convection and the large‐scale radiative forcing, the distribution of boundary‐layer entropy can be linked to the absolute vorticity at the tropopause. According to this analytical theory, the onset of the monsoon, characterized by the ‘jump’, reflects of a nonlinear shift from a radiative‐convective equilibrium regime to an angular momentum conserving regime that would only occur when the value of absolute vorticity in the upper troposphere approaches a threshold of zero. It is because, when the absolute vorticity is significantly different from zero, then the air as a rotating fluid is too rigid to exhibit a meridional overturning. Here, we use the MIT regional climate model (MRCM) to test this theory further and reach a couple of conclusions. First, MRCM succeeds in reproducing the main features of the observed rainfall distribution, including the ‘jump’. Second, analysis of the rainfall, vorticity, entropy, and wind fields simulated by the model reveals a dynamical picture consistent with the proposed theory.
Climatic potential for summer and winter wine production
Authors: de Oliveira Aparecido Lucas Eduardo , Moreto Victor Brunini , de Souza Rolim Glauco , da Silva Cabral de Moraes José Reinaldo , Valeriano Taynara Tuany Borges , de Souza Paulo Sergio
Published: July 2017

BACKGROUND

The geoviticultural multicriteria climatic classification (MCC) system provides an efficient guide for assessing the influence of climate on wine varieties. Paraná is one of the three states in southern Brazil that has great potential for the expansion of wine production, mainly due to the conditions that favour two harvests a year. The objective was to apply the geoviticultural MCC system in two production seasons. We used maximum, mean and minimum air temperature and precipitation for 1990–2015 for the state of Paraná. Air temperature and Precipitation were used to calculate the evapotranspiration and water balance. We applied the MCC system to identify potential areas for grapevine production for harvests in both summer and winter and then determined the climatic zones for each geoviticultural climate.

RESULTS

Paraná has viticultural climates with conditions favourable for grapevine cultivation for the production of fine wines from summer and winter harvests. The conditions for the winter harvest provided wines with good coloration and high aromatic potential relative to the summer harvest.

CONCLUSION

Chardonnay, Merlot, Pinot Blanc and Müller‐Thurgau were suitable for regions with lower air temperatures and water deficits. Pinot Blanc and Müller‐Thurgau were typical for the southern region of Paraná. © 2017 Society of Chemical Industry
Factors predictive of occult nipple‐areolar complex involvement in patients with carcinoma in situ of the breast
Authors: Hwang Hyeoseong , Park Seho , Koo Ja Seung , Park Hyung Seok , Kim Seung Il , Cho Young Up , Park Byeong‐Woo , Yoon Jung Hyun , Kim Min Jung , Kim Eun‐Kyung
Published: July 2017

Objectives

To investigate predictors of occult nipple‐areolar complex (NAC) involvement in patients with carcinoma in situ (CIS) and to validate an online probability calculator (CancerMath; www.lifemath.net/cancer/breastcancer/nipplecalc/index.php).

Methods

Mastectomized patients with CIS (n = 104) were retrospectively selected. Clinicopathology and preoperative mammography, ultrasound, and magnetic resonance imaging (MRI) findings were analyzed.

Results

Histopathological NAC‐positivity was confirmed in 20 (19.2%) patients. Short nipple‐tumor distance and suspicious extension to the nipple by mammography were significant but ultrasound was not significant to predict NAC involvement. NAC‐positive cases had MRI findings of shorter nipple‐tumor distance in both the early and delayed phases. Multivariable regression model showed age >50 years and shorter tumor‐nipple distance on the delay phase of MRI were statistically significant predictors of NAC involvement. Area under the receiver operating characteristics curve (AUC) was 0.618 when calculated by CancerMath; however, an AUC of 0.954 was achieved when distance and age were applied together as predictor.

Conclusions

Mammographic and MRI findings were significant for predicting NAC involvement, with distance of the tumor from the nipple in delay phase MRI the most significant predictor of NAC involvement. Therefore, breast MRI could be beneficial for planning nipple‐sparing mastectomy in patients with CIS.
Preoperative bevacizumab and volumetric recovery after resection of colorectal liver metastases
Authors: Margonis Georgios Antonios , Buettner Stefan , Andreatos Nikolaos , Sasaki Kazunari , Pour Manijeh Zargham , Deshwar Ammar , Wang Jane , Ghasebeh Mounes Aliyari , Damaskos Christos , Rezaee Neda , Pawlik Timothy M. , Wolfgang Christopher L. , Kamel Ihab R. , Weiss Matthew J.
Published: July 2017

Background and Objectives

While preoperative treatment is frequently administered to CRLM patients, the impact of chemotherapy, with or without bevacizumab, on liver regeneration remains controversial.

Methods

The early and late regeneration indexes were defined as the relative increase in liver volume (RLV) within 2 and 9 months from surgery. Regeneration rates of the preoperative treatment groups were compared.

Results

Preoperative chemotherapy details and volumetric data were available for 185 patients; 78 (42.2%) received preoperative chemotherapy with bevacizumab (Bev+), 46 (24.8%) received chemotherapy only (Bev−), and 61 (33%) received no chemotherapy. Patients in the Bev+ and Bev− groups received similar chemotherapy cycles (4 [3‐6] vs 4 [4‐6]; P = 0.499). Despite the comparable clinicopathological characteristics and Resected Volume/Total Liver Volume (TLV) at surgery (P = 0.944) of both groups, Bev+ group had higher early and late regeneration (17.2% vs 4.3%; P = 0.035 and 14.0% vs 9.4%; P = 0.091, respectively). Of note, early and late regeneration rates (3.7% and 10.9% vs 6.6% and 5.5%, respectively) were comparable between the no chemotherapy and Bev− groups (all P > 0.05). In multivariable analysis —adjusted for gender, age, portal vein embolization, preoperative chemotherapy, resected liver volume, tumor number, postoperative chemotherapy, fibrosis, steatosis— bevacizumab independently predicted early liver regeneration (P = 0.019).

Conclusion

Our findings suggest that preoperative bevacizumab administered along with chemotherapy was associated with enhanced volumetric restoration. Interestingly, this effect was more pronounced among patients who received oxaliplatin‐based regimens and bevacizumab compared to those treated with irinotecan‐based regimens and bevacizumab.
Gender Differences in Machine Learning Models of Trauma and Suicidal Ideation in Veterans of the Iraq and Afghanistan Wars
Authors: Gradus Jaimie L. , King Matthew W. , Galatzer‐Levy Isaac , Street Amy E.
Published: July 2017

Suicide rates among recent veterans have led to interest in risk identification. Evidence of gender‐and trauma‐specific predictors of suicidal ideation necessitates the use of advanced computational methods capable of elucidating these important and complex associations. In this study, we used machine learning to examine gender‐specific associations between predeployment and military factors, traumatic deployment experiences, and psychopathology and suicidal ideation (SI) in a national sample of veterans deployed during the Iraq and Afghanistan conflicts (n= 2,244). Classification, regression tree analyses, and random forests were used to identify associations with SI and determine their classification accuracy. Findings converged on several associations for men that included depression, posttraumatic stress disorder (PTSD), and somatic complaints. Sexual harassment during deployment emerged as a key factor that interacted with PTSD and depression and demonstrated a stronger association with SI among women. Classification accuracy for SI presence or absence was good based on the receiver operating characteristic area under the curve, men = .91, women = .92. The risk for SI was classifiable with good accuracy, with associations that varied by gender. The use of machine learning analyses allowed for the discovery of rich, nuanced results that should be replicated in other samples and may eventually be a basis for the development of gender‐specific actuarial tools to assess SI risk among veterans.
Genetic Paradoxes in an Italian Family with PARK2 Multiexon Duplication
Authors: Petrucci Simona , Ferrazzano Gina , Ginevrino Monia , Tolve Manuela , Berardelli Isabella , Berardelli Alfredo , Fabbrini Giovanni , Valente Enza Maria
Published: July 2017

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Impact of poly(ɛ‐caprolactone) architecture on the thermomechanical and shape memory properties
Authors: Deshmukh Prashant , Yoon Hyeongho , Cho Seungwan , Yoon Sook Young , Zore Omkar V. , Kim Taeyoon , Chung Ildoo , Ahn Suk‐Kyun , Kasi Rajeswari M.
Published: July 2017

We report the synthesis of linear‐ and brush‐type poly(ɛ‐caprolactone) (PCL) networks and investigate their thermal, mechanical, and shape memory behavior. Brush‐PCLs are prepared by ring‐opening metathesis polymerization (ROMP) of a norbornenyl‐functionalized ɛ‐caprolactone macromonomer (MM‐PCL) of different molecular weights. The linear analog, diacrylate end‐functionalized PCL (linear‐PCL), having comparable molecular weight of side chain of brush‐PCL is also synthesized. These polymers are thermally cured by a radical initiator in the presence of poly(ethylene glycol) diacrylate crosslinker. Thermal and linear viscoelastic properties as well as shape memory performance of the resulting PCL networks are investigated, and are significantly impacted by the PCL architecture. Therefore, our work highlights that tailoring macromolecular architecture is useful strategy to manipulate thermal, mechanical, and resulting shape memory properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3424–3433
NiWO3 Nanoparticles Grown on Graphitic Carbon Nitride (g‐C3N4) Supported Toray Carbon as an Efficient Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions
Authors: Kumar M. Praveen , Murugesan Pramila , Vivek Sankar , Ravichandran Subbiah
Published: July 2017

Catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are at the heart of water oxidation reactions. Despite continuous efforts, the development of OER/HER electrocatalysts with high activity at low cost remains a big challenge. Herein, a composite material consisting of TC@WO3@g‐C3N4@Ni‐NiO complex matrix as a bifunctional electrocatalyst for the OER and HER is described. Though the catalyst has modest activity for HER, it exhibits high OER activity thereby making it a better nonprecious electrocatalyst for both OER and HER and is further improved by g‐C3N4. The catalytic activity arises from the synergetic effects between WO3, Ni‐NiO, and g‐C3N4. A Ni‐NiO alloy and WO3 nanoparticles decorated on the g‐C3N4 surface supported toray carbon (TC) matrix (TC@WO3@g‐C3N4@Ni‐NiO) by a facile route that show an excellent and durable bifunctional catalytic activity for OER and HER in the alkaline medium are developed. This carbon nitride with binary metal/metal‐oxide matrix supported with TC exhibit an overpotential of 0.385 and 0.535 V versus RHE at a current density of 10 mA cm−2 (Tafel slopes of 0.057 and 0.246 V dec−1 for OER and HER, respectively), in 0.1 m NaOH . The catalyst is tested in water electrolysis for 17 h.
The Sedimentation of Colloidal Nanoparticles in Solution and Its Study Using Quantitative Digital Photography
Authors: Midelet Johanna , El‐Sagheer Afaf H. , Brown Tom , Kanaras Antonios G. , Werts Martinus H. V.
Published: July 2017

Sedimentation and diffusion are important aspects of the behavior of colloidal nanoparticles in solution, and merit attention during the synthesis, characterization, and application of nanoparticles. Here, the sedimentation of nanoparticles is studied quantitatively using digital photography and a simple model based on the Mason–Weaver equation. Good agreement between experimental time‐lapse photography and numerical solutions of the model is found for a series of gold nanoparticles. The new method is extended to study for the first time the gravitational sedimentation of DNA‐linked gold nanoparticle dimers as a model system of a higher complexity structure. Additionally, simple formulas are derived for estimating suitable parameters for the preparative centrifugation of nanoparticle solutions.
3D Vertically Aligned CNT/Graphene Hybrids from Layer‐by‐Layer Transfer for Supercapacitors
Authors: Nagelli Enoch A. , Huang Liang , Dai Alvin Q.‐Z. , Du Feng , Dai Liming
Published: July 2017

The exceptional electrical, optical, thermal and mechanical properties make graphene and carbon nanotubes (CNTs) promising for a large variety of applications, including energy storage. In practice, it is higly important to translator these properties associated with the low‐dimensional carbon nanomaterials into bulk materials/devices. Recent theoretical studies have proven that three‐dimensional (3D) pillared architectures, consisting of parallel graphene layers intercalated by vertically aligned carbon nanotubes (VA‐CNTs) in between, possess desriable transport and mechanical properties in all dimensions while maintaining the excellent properties of their building blocks. However, it remains challenging to experimentally realize such 3D pillared graphene/VA‐CNT hybrids. Here, tunable 3D pillared graphene/VA‐CNT architectures are formed by chemical vapor deposition, and a template‐free contact transfer process is presented, involving the hydrophobic‐hydrophobic interactions between graphene and VA‐CNTs. The resultant 3D graphene/VA‐CNT hybrids are demonstrated to be efficient electrode materials for supercapacitors with good performance. This newly‐developed methodology holds great potential for fabricating various 3D architectures with many other materials for a wide range of multifunctional applications, including energy storage, electrical and thermal managements, and flexible electronics.
Antofine suppresses endotoxin‐induced inflammation and metabolic disorder via AMP‐activated protein kinase
Authors: Chou Shao‐Ting , Jung Fang , Yang Shih‐Hsing , Chou Hwei‐Ling , Jow Guey‐Mei , Lin Jau‐Chen
Published: July 2017

The inhibition of activated macrophages has been used to develop anti‐inflammatory agents for therapeutic intervention to human diseases that cause excessive inflammatory responses. Antofine, a phenanthroindolizidine alkaloid, has a potent anti‐inflammatory effect. However, the molecular mechanisms of its anti‐inflammatory activity have not yet been fully detailed. In this study, we comprehensively explored the anti‐inflammatory effects of antofine on endotoxin‐induced inflammation in macrophages using cDNA microarray analysis, thereby elucidating the potential mechanism by which antofine suppresses inflammation. Antofine significantly suppressed the secretion of proinflammatory cytokines such as TNFα and IL‐1β and the production of iNOS in LPS‐activated Raw264.7 macrophage cells. In addition, antofine can suppress the expressions of several inflammation‐related genes (such as ARG‐1, IL1F9, IL‐10, and IL‐33) and extracellular matrix genes (such as TNC and HYAL1), as well as a vasopressor gene (EDN1) in activated macrophage cells, that are induced by LPS stimulation. The gene expression profiles analyzed by GeneMANIA software showed that antofine not only contributed anti‐inflammatory activity but also modulated the cellular metabolism via AMPK. Furthermore, antofine also modulated the activation of AMPK and caspase‐1, the key regulator in inflammasome‐mediated IL‐1β maturation, in activated macrophage cells. In conclusion, these data indicated that antofine potentially can not only contribute an anti‐inflammatory effect but can also attenuate the metabolic disorders induced by inflammation via AMPK.
Properties of GaN nanowires with ScxGa1−xN insertion
Authors: Bao A. , Goff L. E. , Zhu T. , Sahonta S.‐L. , Ritchie D. A. , Joyce H. J. , Moram M. A. , Oliver R. A.
Published: July 2017

We report the first GaN nanowire structure incorporating a GaN/ScxGa1–xN axial heterostructure. A 20 nm ScxGa1−xN layer was inserted into GaN nanowires grown by a catalyst‐free self‐assembled method using plasma‐assisted molecular beam epitaxy (PA‐MBE). The insertion was characterised by energy dispersive X‐ray spectroscopy in the scanning transmission electron microscope (STEM‐EDX). High resolution electron microscopy revealed the ScxGa1−xN to have a wurtzite crystal structure as expected at this composition. Cathodoluminescence (CL) imaging in the scanning electron microscope (SEM) at 77 K revealed an emission peak at 377 nm which is not present in samples without the ScxGa1−xN insertion. A correlative study using STEM‐EDX and low temperature SEM‐CL indicates a direct link between the 377 nm emission and the ScxGa1−xN insertion. This is tentatively attributed to a type‐II band offset between the GaN and the ScxGa1−xN insertion.
Looking for coherence in science curriculum
Authors: Sikorski Tiffany‐Rose , Hammer David
Published: July 2017

Despite myriad attempts over the years to design curricula with logical ordering and connections, concerns persist that students view science as a body of prescribed information to memorize. In this essay, we argue that attempts to build coherence into the curriculum reflect fundamental and enduring misconceptions about the nature of coherence itself. Using examples of prominent curriculum projects over the past decade, we argue thatpremeditated coherence, the kind of coherence that is planned and designed for students, may inhibit students’ learning to seek coherence for themselves. We conclude with an approach to curriculum and assessment that emphasizes students’ epistemic agency in seeking coherence.
Efficient Reversible Optical Sensing of Water Achieved through the Conversion of H‐Aggregates of a Merocyanine Salt to J‐Aggregates
Authors: Sahoo Priya Ranjan , Prakash Kunal , Kumar Ajeet , Kumar Satish
Published: July 2017

A stable MC (merocyanine)‐spiropyran as p‐toluenesulfonate salt was synthesized. The structure of the merocyanine salt form of the spiropyran was established by using IR, 1H‐NMR, 13C‐NMR, 2D‐NMR and HR‐MS spectroscopic techniques. The MC salt was employed as an optical probe for the detection of trace water content in the organic media using the naked eye, UV‐Visible and fluorescence spectroscopic techniques. The DLS and TEM measurements were used to support the aggregation and disaggregation of the MC salt form. The results established the conversion of H‐ aggregates to J‐ aggregates can be used for the efficient detection of trace water content in organic media. The optical probe was further used to sense and quantify water molecules associated with the metal salts. The probe can be used multiple times for sensing water. The results provide insightful opportunities for practical applications of sensing trace water content in organic solvents and coordinated to metal ions.
Supercritical‐Fluid‐Assisted Decoration of MoS2 @ MWCNTs and Their Superior Performance in the Electrochemical Hydrogen Evolution Reaction
Authors: Thangasamy Pitchai , Ramesh Ammasi , Sathish Marappan
Published: July 2017

We demonstrate a simple, effective, one–pot and environmentally benign supercritical fluid (SCF) process for the decoration of MoS2 nanoparticles over the surafce of the multiwalled carbon nanotubes (MWCNTs‐MoS2) at a short reaction time of 30 min. The formation of MoS2 by decomposition of ammonium tetrathiomolybdate was confirmed by X‐ray diffraction (XRD) analysis. Raman, transmission electron microscopy energy dispersive X‐ray spectroscopy (TEM‐EDX) and X‐ray photoelectron spectroscopic (XPS) analysis further confirms the formation of MoS2 nanoparticles on CNTs during SCF processing. The attachment of MoS2 nanoparticles over CNTs surface were evidently seen in the high‐resolution transmission electron microscopy (HR‐TEM) imaging and elemental mapping analysis. Interestingly, the fabricated MWCNTs‐MoS2 composite exhibited excellent catalytic activity towards hydrogen evolution reaction with a low Tafel slope of 44 mV/dec and high cathodic current density of 10 mA cm−2 at η=214 mV vs. RHE. The observed enhanced catalytic activity is mainly ascribed to the synergistic effect between MoS2 nanoparticles and MWCNTs electrical support.
Preparation of Salicyl Alcohols and 9‐Arylxanthenes Using Sodium Salicylates and Bromo‐Hydrocarbons Mediated by PPh3
Authors: Zhang Jing , Li Ling‐Jie , Tang Yu , Yang Jun , Xu Kai‐Tian , Zhang Yuan‐Ming
Published: July 2017

A highly efficient and convenient Barbier‐Grignard‐type reaction to give salicyl alcohols and novel facile protocol to furnish unsymmetrical 9‐arylxanthenes using sodium salicylates and unactivated bromo‐hydrocarbons are described. Of total 21 synthesized compounds, 18 compounds containing 14 alcohols and 4 9‐arylxanthenes are new compounds. The products were provided in yields among 38–99%. The electronic and steric effects of bromo‐hydrocarbons on the reaction were discussed. Based on experimental results, a plausible mechanism concerning direct formation of salicyl alcohol from salicylate and PhMgBr with the promotion of PPh3 is proposed.
Preparation of Particulate Polymeric Therapeutics for Medical Applications
Authors: Zhuang Jia , Fang Ronnie H. , Zhang Liangfang
Published: July 2017

Particulate therapeutics fabricated from polymeric materials have become increasingly popular over the past several decades. Generally, polymeric systems are easy to synthesize and have tunable parameters, giving them significant potential for wide use in the clinic. They come in many different forms, including nanoparticles, microparticles, and colloidal gels. Here, the current preparation methods for each type of platform are discussed, along with some representative applications. To achieve enhanced performance, lipid coatings and other surface‐modification techniques for introduction of additional functionalities are also mentioned. By outlining the various methods and techniques for their preparation, insights into the utility of these polymeric platforms are provided and their development for biomedical applications further encouraged.
Diallyl trisulfide inhibits cell migration and invasion of human melanoma a375 cells via inhibiting integrin/facal adhesion kinase pathway
Authors: Wang Hsiao‐Chi , Chu Yung‐Lin , Hsieh Shu‐Chen , Sheen Lee‐Yan
Published: July 2017

Melanoma is the leading cause of death from skin disease due to its propensity for metastasis. Studies have shown that integrin‐mediated focal adhesion kinase (FAK) signal pathway is implicated in cell proliferation, survival and metastasis of tumor cells. Our previous results indicated that diallyl trisulfide (DATS) provided its antimelanoma activity via inducing cell cycle arrest and apoptosis. The aim of this study was to explore DATS mediated antimetastatic effect and the corresponding mechanism in human melanoma A375 cells. We found that DATS exhibited an inhibitory effect on the abilities of migration and invasion in A375 cells under noncytotoxic concentrations analyzed by wound healing assays and Matrigel invasion chamber system. DATS attenuated invasion of A375 cells with characteristic of decreased activities and protein expressions of matrix metalloproteinase‐2 (MMP‐2) and MMP‐9. Moreover, DATS exerted an inhibitory effect on cell adhesion of A375 cells, which is in correlation with the change in integrin signaling pathway. Results of Western blotting showed that DATS decreased the levels of several integrin subunits, including α4, α5, αv, β1, β3 and β4. Subsequently, DATS induced a strong decrease in total FAK, phosphorylated FAK Tyr‐397,‐576, −577, and disorganized F‐actin stress fibers, resulting in a nonmigratory phenotype. These results suggest that the antimetastatic potential of DATS for human melanoma cells might be due to the disruption of integrin/FAK signaling pathway.
ASPRE trial: performance of screening for preterm pre‐eclampsia
Authors: Rolnik D. L. , Wright D. , Poon L. C. Y. , Syngelaki A. , O'Gorman N. , de Paco Matallana C. , Akolekar R. , Cicero S. , Janga D. , Singh M. , Molina F. S. , Persico N. , Jani J. C. , Plasencia W. , Papaioannou G. , Tenenbaum‐Gavish K. , Nicolaides K. H.
Published: July 2017

Objective

To examine the performance of screening for preterm and term pre‐eclampsia (PE) in the study population participating in the ASPRE (Combined Multimarker Screening and Randomized Patient Treatment with Aspirin for Evidence‐Based Preeclampsia Prevention) trial.

Methods

This was a prospective first‐trimester multicenter study on screening for preterm PE in 26 941 singleton pregnancies by means of an algorithm that combines maternal factors, mean arterial pressure, uterine artery pulsatility index and maternal serum pregnancy‐associated plasma protein‐A and placental growth factor at 11–13 weeks' gestation. Eligible women with an estimated risk for preterm PE of > 1 in 100 were invited to participate in a double‐blind trial of aspirin (150 mg per day) vs placebo from 11–14 until 36 weeks' gestation, which showed that, in the aspirin group, the incidence of preterm PE was reduced by 62%. In the screened population, the detection rates (DRs) and false‐positive rates (FPRs) for delivery with PE < 37 and ≥ 37 weeks were estimated after adjustment for the effect of aspirin in those receiving this treatment. We excluded 1144 (4.2%) pregnancies because of loss to follow‐up or study withdrawal (n = 716), miscarriage (n = 243) or termination (n = 185).

Results

The study population of 25 797 pregnancies included 180 (0.7%) cases of preterm PE, 450 (1.7%) of term PE and 25 167 (97.6%) without PE. In combined first‐trimester screening for preterm PE with a risk cut‐off of 1 in 100, the DR was 76.7% (138/180) for preterm PE and 43.1% (194/450) for term PE, at screen‐positive rate of 10.5% (2707/25 797) and FPR of 9.2% (2375/25 797).

Conclusion

The performance of screening in the ASPRE study was comparable with that of a study of approximately 60 000 singleton pregnancies used for development of the algorithm; in that study, combined screening detected 76.6% of cases of preterm PE and 38.3% of term PE at a FPR of 10%. Copyright © 2017 ISUOG. Published by John Wiley & Sons Ltd.
Post‐hospitalization Treatment Regimen and Readmission for C. difficile Colitis in Medicare Beneficiaries
Authors: Psoinos Charles M. , Collins Courtney E. , Ayturk M. Didem , Anderson Frederick A. , Santry Heena P.
Published: July 2017

Background

C. difficile (CDI) has surpassed methicillin‐resistant staph aureus as the most common nosocomial infection with recurrence reaching 30% and the elderly being disproportionately affected. We hypothesized that post‐discharge antibiotic therapy for continued CDI treatment reduces readmissions.

Study design

We queried a 5% random sample of Medicare claims (2009–2011 Part A and Part D; n = 864,604) for hospitalizations with primary or secondary diagnosis of CDI. We compared demographics, comorbidities, and post‐discharge CDI treatment (no CDI treatment, oral metronidazole only, oral vancomycin only, or both) between patients readmitted with a primary diagnosis of CDI within 90 days and patients not readmitted for any reason using univariate tests of association and multivariable models.

Results

Of 7042 patients discharged alive, 945 were readmitted ≤90 days with CDI (13%), while 1953 were not readmitted for any reason (28%). Patients discharged on dual therapy had the highest rates of readmission (50%), followed by no post‐discharge CDI treatment (43%), vancomycin only (28%), and metronidazole only (19%). Patients discharged on only metronidazole (OR 0.28) or only vancomycin (OR 0.42) had reduced odds of 90‐day readmission compared to patients discharged on no CDI treatment. Patients discharged on dual therapy did not vary in odds of readmission.

Conclusions

Thirteen percent of patients discharged with CDI are readmitted within 90 days. Patients discharged with single‐drug therapy for CDI had lower readmission rates compared to patients discharged on no ongoing CDI treatment suggesting that short‐term monotherapy may be beneficial in inducing eradication and preventing relapse. Half of patients requiring dual therapy required readmission, suggesting patients with symptoms severe enough to warrant discharge on dual therapy may benefit from longer hospitalization.
A Novel Prognostic Scoring System Using Inflammatory Response Biomarkers for Esophageal Squamous Cell Carcinoma
Authors: Hirahara Noriyuki , Tajima Yoshitsugu , Fujii Yusuke , Yamamoto Tetsu , Hyakudomi Ryoji , Hirayama Takanori , Taniura Takahito , Ishitobi Kazunari , Kidani Akihiko , Kawabata Yasunari
Published: July 2017

Background

We describe a novel scoring system, namely the inflammatory response biomarker (IRB) score. The aim of this study is to evaluate the clinical value of IRB score in patients undergoing curative resection for esophageal squamous cell carcinoma (SCC).

Methods

We retrospectively reviewed patients who underwent curative esophagectomy. We evaluated IRB score in both non‐elderly (<70 years) and elderly (≥70 years) SCC patients. The IRB score was determined as follows: a high lymphocyte‐to‐monocyte ratio (LMR) (>4), a high neutrophil‐to‐lymphocyte ratio (NLR) (>1.6), and a low platelet‐to‐lymphocyte ratio (PLR) (<147) were each scored as 1, and the remaining values were scored as 0; the individual scores were then summed to produce the IRB score (range 0−3).

Results

Univariate analyses demonstrated that the TNM pStage (p < 0.0001), tumor size (p = 0.002), LMR (p = 0.0057), PLR (p = 0.0328) and IRB score (p = 0.0003) were significant risk factors for a worse prognosis. On multivariate analysis, the TNM pStage (p < 0.0001) and IRB score (p = 0.0227) were independently associated with worse prognosis in overall patients. Among non‐elderly patients, multivariate analyses demonstrated that the pStage (p = 0.0015) and IRB score (p = 0.0356) were independent risk factors for a worse prognosis. Among elderly patients, multivariate analysis demonstrated that the pStage (p = 0.0016), and IRB score (p = 0.0102) were independent risk factors for a worse prognosis.

Conclusion

The present study provides evidence that the preoperative IRB score can be considered a promising independent prognostic factor of cancer‐specific survival in patients undergoing curative resection for SCC, and that its predictive ability is useful in both non‐elderly and elderly patients.