bluuebunny/crossref_metadata_2025 huggingface dataset:
The Renaissance of Non‐Aqueous Uranium Chemistry
Authors: Liddle Stephen T.
Published: June 2015

Prior to the year 2000, non‐aqueous uranium chemistry mainly involved metallocene and classical alkyl, amide, or alkoxide compounds as well as established carbene, imido, and oxo derivatives. Since then, there has been a resurgence of the area, and dramatic developments of supporting ligands and multiply bonded ligand types, small‐molecule activation, and magnetism have been reported. This Review 1) introduces the reader to some of the specialist theories of the area, 2) covers all‐important starting materials, 3) surveys contemporary ligand classes installed at uranium, including alkyl, aryl, arene, carbene, amide, imide, nitride, alkoxide, aryloxide, and oxo compounds, 4) describes advances in the area of single‐molecule magnetism, and 5) summarizes the coordination and activation of small molecules, including carbon monoxide, carbon dioxide, nitric oxide, dinitrogen, white phosphorus, and alkanes.
Short and Divergent Total Synthesis of (+)‐Machaeriol B, (+)‐Machaeriol D, (+)‐Δ8‐THC, and Analogues
Authors: Klotter Felix , Studer Armido
Published: June 2015

Short and highly efficient stereoselective syntheses provide machaeriols and cannabinoids in a divergent approach starting from a common precursor, commercially available (S)‐perillic acid. Key features of the novel strategy are a stereospecific palladium‐catalyzed decarboxylative arylation and a one‐pot sequence comprising a stereoselective hydroboration followed by oxidation or reduction of the corresponding intermediary boranes. The divergent approach is convincingly demonstrated by the five‐step syntheses of (+)‐machaeriol B, (+)‐machaeriol D, and related analogues, and the four‐step synthesis of (+)‐Δ8‐THC and an analogue.
Self‐Healing, Expansion–Contraction, and Shape‐Memory Properties of a Preorganized Supramolecular Hydrogel through Host–Guest Interactions
Authors: Miyamae Kohei , Nakahata Masaki , Takashima Yoshinori , Harada Akira
Published: June 2015

Supramolecular materials cross‐linked between polymer chains by noncovalent bonds have the potential to provide dynamic functions that are not produced by covalently cross‐linked polymeric materials. We focused on the formation of supramolecular polymeric materials through host–guest interactions: a powerful method for the creation of nonconventional materials. We employed two different kinds of host–guest inclusion complexes of β‐cyclodextrin (βCD) with adamantane (Ad) and ferrocene (Fc) to bind polymers together to form a supramolecular hydrogel (βCD‐Ad‐Fc gel). The βCD‐Ad‐Fc gel showed self‐healing ability when damaged and responded to redox stimuli by expansion or contraction. Moreover, the βCD‐Ad‐Fc gel showed a redox‐responsive shape‐morphing effect. We thus succeeded in deriving three functions from the introduction of two kinds of functional units into a supramolecular material.
CD47 is an adverse prognostic factor and a therapeutic target in gastric cancer
Authors: Yoshida Kazumichi , Tsujimoto Hironori , Matsumura Kouji , Kinoshita Manabu , Takahata Risa , Matsumoto Yusuke , Hiraki Shuichi , Ono Satoshi , Seki Shuhji , Yamamoto Junji , Hase Kazuo
Published: June 2015

CD47 is an antiphagocytic molecule that acts via ligation to signal regulatory protein alpha on phagocytes; its enhanced expression and therapeutic targeting have recently been reported for several malignancies. However, CD47 expression in gastric cancer is not well documented. Immunohistochemical expression of CD47 in surgical specimens was investigated. Expression of CD47 and CD44, a known gastric cancer stem cell marker, were investigated in gastric cancer cell lines by flow cytometry. MKN45 and MKN74 gastric cancer cells were sorted by fluorescence‐activated cell sorting according to CD44 and CD47 expression levels, and their in vitro proliferation, spheroid‐forming capacity, and in vivo tumorigenicity were studied. In vitro phagocytosis of cancer cells by human macrophages in the presence of a CD47 blocking monoclonal antibody (B6H12) and the survival of immunodeficient mice intraperitoneally engrafted with MKN45 cells and B6H12 were compared to experiments using control antibodies. Immunohistochemistry of the clinical specimens indicated that CD47 was positive in 57 out of 115 cases, and its positivity was an independent adverse prognostic factor. Approximately 90% of the MKN45 and MKN74 cells expressed CD47 and CD44. CD47hi gastric cancer cells showed significantly higher proliferation and spheroid colony formation than CD47lo, and CD44hiCD47hi cells showed the highest proliferation in vitro and tumorigenicity in vivo. B6H12 significantly enhanced in vitro phagocytosis of cancer cells by human macrophages and prolonged the survival of intraperitoneal cancer dissemination in mice compared to control antibodies. In conclusion, CD47 is an adverse prognostic factor and promising therapeutic target in gastric cancer.
Genome Mining for Innovative Biocatalysts: New Dihydroxyacetone Aldolases for the Chemist’s Toolbox
Authors: Guérard‐Hélaine Christine , de Berardinis Véronique , Besnard‐Gonnet Marielle , Darii Ekaterina , Debacker Marine , Debard Adrien , Fernandes Carlos , Hélaine Virgil , Mariage Aline , Pellouin Virginie , Perret Alain , Petit Jean‐Louis , Sancelme Martine , Lemaire Marielle , Salanoubat Marcel
Published: June 2015

Stereoselective carboligating enzymes were discovered by a genome mining approach to extend the biocatalysis toolbox. Seven hundred enzymes were selected by sequence comparison from diverse prokaryotic species as representatives of the aldolase (FSA) family diversity. The aldol reaction tested involved dihydroxyacetone (DHA) and glyceraldehyde‐3‐phosphate. The hexose‐6‐phosphate formation was monitored by mass spectrometry. Eighteen enzymes annotated either as transaldolases or aldolases were found to exhibit a DHA aldolase activity. Remarkably, six of them proven as aldolases, and not transaldolases, shared very limited similarities with those currently described. Multiple sequence alignment performed on all enzymes revealed a Tyr in the new DHA aldolases as found in FSAcoli instead of a Phe usually found in transaldolases. Four of these DHA aldolases were biochemically characterised in comparison with FSAcoli. In particular, an aldolase from Listeria monocytogenes exhibited interesting catalytic properties.
Chemoenzymatic Synthesis of ortho‐, meta‐, and para‐Substituted Derivatives of L‐threo‐3‐Benzyloxyaspartate, An Important Glutamate Transporter Blocker
Authors: de Villiers Jandré , de Villiers Marianne , Geertsema Edzard M. , Raj Hans , Poelarends Gerrit J.
Published: June 2015

A simple, three‐step chemoenzymatic synthesis of L‐threo‐3‐benzyloxyaspartate (L‐TBOA), as well as L‐TBOA derivatives with F, CF3, and CH3 substituents at the aromatic ring, starting from dimethyl acetylenedicarboxylate was investigated. These chiral amino acids, which are extremely difficult to prepare by chemical synthesis, form an important class of inhibitors of excitatory amino acid transporters involved in the regulation of glutamatergic neurotransmission. In addition, a new chemical procedure for the synthesis of racemic mixtures of TBOA and its derivatives was explored. These chemically prepared racemates are valuable reference compounds in chiral‐phase HPLC to establish the enantiopurities of the corresponding chemoenzymatically prepared amino acids.
Low‐Temperature Selective Catalytic Reduction of NO on an Iron Ore Catalyst in a Magnetically Fluidized Bed
Authors: Gui Keting , Liang Hui , Wang Fang , Wang Xiaobo , Yao Guihuan
Published: June 2015

Low‐temperature selective catalytic reduction of NO from simulated flue gas by NH3 on admixtures of iron ore and iron catalyst in a magnetically fluidized bed was experimentally studied. It was found that iron ore exerts a prominent catalytic effect on NO removal resulting in high removal efficiency without magnetic fields. Since iron ore is insensitive to magnetic fields due to its antiferromagnetic property, NO removal efficiency with iron ore as catalyst is only slightly influenced by magnetic fields. The NO removal efficiency, however, can be greatly improved using admixtures of iron ore and iron as catalyst in a magnetically fluidized bed. At defined magnetic field intensity and the same temperature, the removal efficiency reaches higher values compared with that without magnetic fields.
Breakage and Particle Size Redistribution in an Ultrasound‐Intensified Leaching Process
Authors: Gao Jiang Xiong , Huang Hou Quan , Li Xiao Xia , Du Fei Hu , Li Lin Bo , Li Jing Sheng
Published: June 2015

The breakage and particle size redistributions in an ultrasound‐intensified leaching process were explored experimentally and analyzed statistically. It was found that particle size distributions (PSDs) of this atomic crystal silica may be changed to a certain extent by ultrasound, but the width of PSD cannot be altered under the conditions considered. Chemical reactions played an important reciprocal causality to the breakage and the particle size redistributions, and the contribution was about a half on the mean particle size. The most severe breakup happened at the maximum volume percentage of PSD rather than in the region of the largest particle size end. The ability of conventional stirring to break the silica particles may be larger as expected when the same power was used. The morphology of the silica particles verified that the change before and after leaching is small.
Synthesis and Characterization of Ba[CoSO]: Magnetic Complexity in the Presence of Chalcogen Ordering
Authors: Valldor Martin , Rößler Ulrich K. , Prots Yurii , Kuo Chang‐Yang , Chiang Jen‐Che , Hu Zhiwei , Pi Tun‐Wen , Kniep Rüdiger , Tjeng Liu Hao
Published: June 2015

Barium thio‐oxocobaltate(II), Ba[CoS2/2O2/2], was synthesized by the reaction of equimolar amounts of BaO, Co, and S in closed silica ampoules. The title compound (Cmcm, a=3.98808(3), b=12.75518(9), c=6.10697(4) Å) is isostructural to Ba[ZnSO]. The use of soft X‐ray absorption spectroscopy confirmed that cobalt is in the oxidation state +2 and tetrahedrally coordinated. Its coordination consists of two sulfur and two oxygen atoms in an ordered fashion. High‐temperature magnetic susceptibility data indicate strong low‐dimensional spin–spin interactions, which are suggested to be closely related to the layer‐type crystal structure and perhaps the ordered distribution of sulfur and oxygen. Antiferromagnetic ordering below TN=222 K is observed as an anomaly in the specific heat, coinciding with a significant lowering of the magnetic susceptibility. Density functional theory calculations within a generalized‐gradient approximation (GGA)+U approach identify an antiferromagnetic ground state within the square‐like two‐dimensional layers of Co, and antiferromagnetic correlations for nearest and next nearest neighbors along bonds mediated by oxygen or sulfur. However, this magnetic state is subject to frustration by relatively strong interlayer couplings.
Hierarchical Porous ZnMn2O4 Hollow Nanotubes with Enhanced Lithium Storage toward Lithium‐Ion Batteries
Authors: Zhang Longhai , Zhu Siqi , Cao Hui , Hou Linrui , Yuan Changzhou
Published: June 2015

We have purposefully developed a smart template‐engaged methodology to efficiently fabricate well‐defined ternary spinel ZnMn2O4 hollow nanotubes (NTs). The procedure involves coating carbon nanotubes (CNTs) with ZnMn2O4 nanosheets (NSs), followed by heating at high temperature in air to oxidize the CNT template. Physicochemical characterization demonstrated that the formed ZnMn2O4 NTs with a diameter of approximately 100 nm were composed of assembled NSs and/or nanoparticles (NPs) as building blocks and possessed numerous nanopores of several nanometers in the sidewall of the NTs. In favor of the intrinsic structural advantages, the resulting ZnMn2O4 NTs exhibited superior electrochemical lithium‐storage performance with a large capacity, good rate behavior, and excellent cyclability when evaluated as promising anodes for lithium‐ion batteries (LIBs). The remarkable electrochemical performance was rationally ascribed to the appealing one‐dimensional (1D) porous hollow tubular architecture with nanoscale subunits and mesopores in the sidewalls, which decreased the diffusion length for the Li+ ions, improved the kinetic process, and enhanced the structural integrity with sufficient void space to tolerate the volume variation during Li+‐ion insertion/extraction. These results highlight the promising application of 1D ZnMn2O4 NTs as anodes for high‐performance LIBs.
Stereoselective Synthesis of (R)‐3‐Methylthalidomide by Piperidin‐2‐one Ring Assembly Approach
Authors: Yadav Shyam Raj , Tiwari Vinay Shankar , Haq Wahajul
Published: June 2015

A simple and stereoselective synthesis of 3‐methylthalidomide, a configurationally stable thalidomide analog, is presented. Herein we describe the synthesis of (R)‐3‐methylthalidomide starting from (S)‐alanine by piperidin‐2‐one ring assembly approach in high yield and enantiomeric purity without using a chiral auxiliary or reagent. Starting from (R)‐alanine, the corresponding (S)‐3‐methylthalidomide can be prepared using the same methodology. Chirality 27:619–624, 2015. © 2015 Wiley Periodicals, Inc.
Numerical Study of Gas‐Liquid Flow in Dual‐Contact‐Flow Absorber with One‐Dimensional Two‐Way Coupled Model
Authors: Zhang Yafei , Li Na , Wang Duanyang , Zhou Qulan , Chen Xi
Published: June 2015

The dual‐contact‐flow absorber is widely used in gas‐liquid reactions, such as wet flue gas desulfurization process. Yet the exemplification of the micro‐mechanisms of the flow, heat, and mass transfer of a liquid droplet swarm in the absorber is still lacking. Based on the industrial principles of high efficiency and practicability, a one‐dimensional two‐way coupled model is established in this paper, in order to study the micro‐mechanisms of gas‐liquid flow in a dual‐contact‐flow absorber. By incorporating the discrete phase, the liquid density distribution, as well as the heat and mass transfer of the liquid particle swarm, are obtained under different liquid initial jetting velocities and empty cross‐sectional gas velocities. In addition, the simulation results have been verified by parallel experiment data. The results indicate that the height of the liquid bed is mainly decided by the liquid initial jetting velocities. It has also been found that the top of the liquid bed where the highest heat transfer appears will hold the greatest number of liquid droplets; thus it is essential to choose a proper initial jetting velocity in applications. The most intense mass transfer area, unlike the heat transfer in this manuscript, is at the bottom of the absorber where the liquid is injected from the nozzles. The empty cross‐sectional gas velocity determines what size of liquid droplets will be carried away by the gaseous phase from the top of the absorber. The study may provide useful guidelines for dual‐contact‐flow absorber design and applications.
Biodiesel Production using CaO/γ‐Al2O3 Catalyst Synthesized by Sol‐Gel Method
Authors: Moradi Gholamreza , Mohadesi Majid , Rezaei Raziye , Moradi Ramin
Published: June 2015

In this study, 40 % CaO/γ‐Al2O3 catalyst was used for biodiesel production from corn oil. A transesterification reaction was done for 5 h at a temperature of 65 °C in the presence of corn oil, methanol (methanol to oil molar ratio of 12:1), and CaO/γ‐Al2O3 catalyst (0.06 g/g (6 wt%)). Catalyst used in this study was synthesized using the sol‐gel method. In this method, two parameters of gelation temperature and nitric acid concentration were used as variables in the catalyst synthesis step, and experiments were designed using central composite design (CCD). The results indicate that the optimal point is achieved at a gelation temperature of 70 °C and nitric acid concentration of 0.050 mol/L; in such conditions the purity and yield of produced biodiesel are 87.89 % and 79.10 %, respectively. Moreover, 40 % CaO/γ‐Al2O3 catalyst was synthesized using the impregnation method and the same reaction conditions were used. The catalyst synthesized by the sol‐gel method in optimal conditions and catalyst synthesized by impregnation method both were reused five times each. Catalyst reuse reduces the purity and yield of the produced biodiesel, because in each case of catalyst use, some amount of CaO is extracted by methanol. In addition, the leaching rate of CaO in the catalyst synthesized by the impregnation method was greater than that of the catalyst synthesized by the sol‐gel method; consequently there is more reduction the activity of the catalyst synthesized by impregnation method.
Trends in surveillance for resected colorectal cancer, 2001‐2009
Authors: Paulson E. Carter , Veenstra Christine M. , Vachani Anil , Ciunci Christine A. , Epstein Andrew J.
Published: June 2015

BACKGROUND

Little is known about recent trends in surveillance among the more than 1 million US colorectal cancer (CRC) survivors. Moreover, for stage I disease, which accounts for more than 30% of survivors, the guidelines are limited, and the use of surveillance has not been well studied. Guidelines were changed in 2005 to include recommendations for computed tomography (CT) surveillance in select patients, but the impact of these changes has not been explored.

METHODS

A retrospective analysis of patients who were identified in the Survival, Epidemiology, and End Results–Medicare database and underwent resection of stage I to III CRC between 2001 and 2009 was performed. The receipt of guideline‐determined sufficient surveillance, including office visits, colonoscopy, carcinoembryonic antigen (CEA) testing, and CT imaging, in the 3 years after resection was evaluated.

RESULTS

The study included 23,990 colon cancer patients and 5665 rectal cancer patients. Rates of office visits and colonoscopy were high and stable over the study period. Rates of CEA surveillance increased over the study period but remained low, even for stage III disease. Rates of CT imaging increased gradually during the study period, but the 2005 guideline change had no effect. Stage II patients, including high‐risk patients, received surveillance at significantly lower rates than stage III patients despite similar recommendations. Conversely, up to 30% of stage I patients received nonrecommended CEA testing and CT imaging.

CONCLUSIONS

There continues to be substantial underuse of surveillance for CRC survivors and particularly for stage II patients, who constitute almost 40% of survivors. The 2005 guideline change had a negligible impact on CT surveillance. Conversely, although guidelines are limited, many stage I patients are receiving intensive surveillance. Cancer 2015;121:3435–43. © 2015 American Cancer Society.
Impact of hepatitis C virus eradication on hepatocellular carcinogenesis
Authors: Li Darrick K. , Chung Raymond T.
Published: June 2015

Hepatocellular carcinoma (HCC) is one of the leading causes of cancer‐related death in the world. Infection with hepatitis C virus (HCV) represents one of the most common risk factors for HCC development, and cases of HCV‐related complications have been rising over the last 2 decades. Although the standard for HCV therapy has been interferon (IFN)‐based for many years, the therapeutic revolution spurred by the development of direct‐acting antivirals (DAAs) promises to usher in a new era in which chronic HCV becomes a rare disease. On the basis of long‐term follow‐up of patients experiencing IFN‐based sustained virological responses (SVRs), it can be expected that rates of HCV‐associated HCC will decrease significantly after the widespread adoption of DAAs, but there remains a persistent risk for HCC even among some patients with advanced fibrosis who have achieved SVR. As such, individuals treated for HCV with advanced fibrosis should continue to be screened regularly for HCC after SVR. Furthermore, as the population of SVR patients grows, it will become imperative to accurately identify those individuals at high risk for developing HCC, appropriately allocate resources for screening, and consider cost‐effective chemopreventive strategies. Risk factors include preexisting advanced fibrosis/cirrhosis, older age, diabetes mellitus, and ethanol use. In addition, laboratory biomarkers and genetic signatures are currently being identified that not only predict the likelihood of HCC development in SVR patients but also may serve as dynamic indicators of therapeutic response. Cancer 2015;121:2874–2882. © 2015 American Cancer Society.
Use of BRAF v600e immunocytochemistry on FNA direct smears of papillary thyroid carcinoma
Authors: Wobker Sara E. , Kim Lawrence T. , Hackman Trevor G. , Dodd Leslie G.
Published: June 2015

BACKGROUND

Mutations of v‐Raf murine sarcoma viral oncogene homolog B1 (BRAF) are identified in almost half of all papillary thyroid carcinomas (PTCs). These mutations are specific for PTC and may confer a worse prognosis. An immunohistochemical (IHC) stain for BRAF is commercially available and has been validated in surgical specimens. Fine‐needle aspiration (FNA) is frequently used as a diagnostic tool for risk stratification of thyroid nodules. Therefore, the authors evaluated the performance of immunostaining with the anti‐BRAF antibody VE1 on FNA direct smears.

METHODS

The authors identified 51 FNA specimens that had subsequent surgical resection specimens with a diagnosis of PTC. BRAF VE1 IHC was performed on the surgical specimens to determine their mutation status. The corresponding direct smears were then stained using the same VE1 stain to assess correlation.

RESULTS

Twenty‐two of the 46 included surgical specimens were positive for BRAF mutations (47.8%) by IHC, consistent with the published rates. The paired cytologic smears from these cases revealed 65.3% concordance. The overall sensitivity of BRAF staining on cytologic smears was 63.6%, and the specificity was 58.3%. Concordance rates were highest in specimens that were diagnosed as malignant or suspicious for malignancy (75% and 85.7%, respectively). The negative predictive value increased to 77.8% when suspicious for follicular neoplasm/suspicious cases were combined.

CONCLUSIONS

Specimens that were malignant or suspicious on FNA were most likely to be BRAF concordant. Limitations to the interpretation of smears included low cellularity and obscuring blood, macrophages, or colloid. With further refinement, it is possible that BRAF immunocytochemistry can be applied prospectively to thyroid FNAs for risk stratification and to reduce false‐negative rates. Cancer (Cancer Cytopathol) 2015;123:531–539. © 2015 American Cancer Society.
Improvement in Hydrogen Desorption from β‐ and γ‐MgH2 upon Transition‐Metal Doping
Authors: Hussain Tanveer , Maark Tuhina Adit , Chakraborty Sudip , Ahuja Rajeev
Published: June 2015

A thorough study of the structural, electronic, and hydrogen‐desorption properties of β‐ and γ‐MgH2 phases substituted by selected transition metals (TMs) is performed through first‐principles calculations based on density functional theory (DFT). The TMs considered herein include Sc, V, Fe, Co, Ni, Cu, Y, Zr, and Nb, which substitute for Mg at a doping concentration of 3.125 % in both the hydrides. This insertion of TMs causes a variation in the cell volumes of β‐ and γ‐MgH2. The majority of the TM dopants decrease the lattice constants, with Ni resulting in the largest reduction. From the formation‐energy calculations, it is predicted that except for Cu and Ni, the mixing of all the selected TM dopants with the MgH2 phases is exothermic. The selected TMs also influence the stability of both β‐ and γ‐MgH2 and cause destabilization by weakening the MgH bonds. Our results show that doping with certain TMs can facilitate desorption of hydrogen from β‐ and γ‐MgH2 at much lower temperatures than from their pure forms. The hydrogen adsorption strengths are also studied by density‐of‐states analysis.
Electron Transfer across Helical Peptides
Authors: Amdursky Nadav
Published: June 2015

Electron transfer (ET) across proteins is one of the fundamental processes in nature. While trying to decipher and understand natural ET, much scientific effort has been employed in scaling down the process to the role of the elementary secondary‐structure units of proteins, that is, β sheets and α helices. Among these two motifs, the vast majority of studies have focused on α‐helical peptides because they require fewer amino acids for formation, they can be easily assembled on surfaces, and they can be easily functionalized. Herein, the focus is only on ET across α‐helical peptides, not only because of the reasons discussed, but also because they are one of the most promising biological molecules for integration into ET‐based bioelectronic devices. The different methodologies used to follow ET across the peptides, namely, photoinduced ET, electrochemistry, and solid‐state conductivity measurements (referred to as electron transport, ETp), are reviewed and discussed. In this context, the fundamental differences between the different methodologies, the appropriate interpretation of the results, and possible mechanisms to describe the ET(p) process in each methodology are discussed. Furthermore, possible functionalization of the helical peptides to modify and control their (opto‐)electronic properties is reviewed.
Towards Stable Lithium–Sulfur Batteries with a Low Self‐Discharge Rate: Ion Diffusion Modulation and Anode Protection
Authors: Xu Wen‐Tao , Peng Hong‐Jie , Huang Jia‐Qi , Zhao Chen‐Zi , Cheng Xin‐Bing , Zhang Qiang
Published: June 2015

The self‐discharge of a lithium–sulfur cell decreases the shelf‐life of the battery and is one of the bottlenecks that hinders its practical applications. New insights into both the internal chemical reactions in a lithium–sulfur system and effective routes to retard self‐discharge for highly stable batteries are crucial for the design of lithium–sulfur cells. Herein, a lithium–sulfur cell with a carbon nanotube/sulfur cathode and lithium‐metal anode in lithium bis(trifluoromethanesulfonyl)imide/1,3‐dioxolane/dimethyl ether electrolyte was selected as the model system to investigate the self‐discharge behavior. Both lithium anode passivation and polysulfide anion diffusion suppression strategies are applied to reduce self‐discharge of the lithium–sulfur cell. When the lithium‐metal anode is protected by a high density passivation layer induced by LiNO3, a very low shuttle constant of 0.017 h−1 is achieved. The diffusion of the polysulfides is retarded by an ion‐selective separator, and the shuttle constants decreased. The cell with LiNO3 additive maintained a discharge capacity of 97 % (961 mAh g−1) of the initial capacity after 120 days at open circuit, which was around three times higher than the routine cell (32 % of initial capacity, corresponding to 320 mAh g−1). It is expected that lithium–sulfur batteries with ultralow self‐discharge rates may be fabricated through a combination of anode passivation and polysulfide shuttle control, as well as optimization of the lithium–sulfur cell configuration.
Classification of blood cells and tumor cells using label‐free ultrasound and photoacoustics
Authors: Strohm Eric M. , Kolios Michael C.
Published: June 2015

A label‐free method that can identify cells in a blood sample using high frequency photoacoustic and ultrasound signals is demonstrated. When the wavelength of the ultrasound or photoacoustic wave is similar to the size of a single cell (frequencies of 100–500 MHz), unique periodic features occur within the ultrasound and photoacoustic power spectrum that depend on the cell size, structure, and morphology. These spectral features can be used to identify different cell types present in blood, such as red blood cells (RBCs), white blood cells (WBCs), and circulating tumor cells. Circulating melanoma cells are ideal for photoacoustic detection due to their endogenous optical absorption properties. Using a 532 nm pulsed laser and a 375 MHz transducer, the ultrasound and photoacoustic signals from RBCs, WBCs, and melanoma cells were individually measured in an acoustic microscope to examine how the signals change between cell types. A photoacoustic and ultrasound signal was detected from RBCs and melanoma cells; only an ultrasound signal was detected from WBCs. The different cell types were distinctly separated using the ultrasound and photoacoustic signal amplitude and power spectral periodicity. The size of each cell was also estimated from the spectral periodicity. For the first time, sound waves generated using pulse‐echo ultrasound and photoacoustics have been used to identify and size single cells, with applications toward counting and identifying cells, including circulating melanoma cells. © 2015 International Society for Advancement of Cytometry
Marginal quality‐based long‐term incentive mechanisms for crowd sensing
Authors: Sun Jiajun
Published: June 2015

Crowd sensing is a new paradigm that leverages pervasive sensor‐equipped mobile devices to provide sensing services like forensic analysis, documenting public spaces, and collaboratively constructing statistical models. Extensive user participation is indispensable for achieving good service quality. Nowadays, most of existing mechanisms focus on guaranteeing good service quality based on instantaneous extensive user participation for crowd sensing applications. Little attention has been dedicated to maximizing long‐term service quality for crowd sensing applications due to their heterogeneous interests, preferences, selfish behaviors, and so on. To fill these gaps, a closed‐form expression of the marginal sensing data quality based on the monopoly aggregation in economics is derived in this paper. Furthermore, we design marginal quality‐based incentive mechanisms for long‐term crowd sensing applications not only to enhance extensive user participation by maximizing the expected total profits of mobile users but also to stimulate mobile users to produce high‐quality contents by applying the marginal quality. Finally, simulation results show that our mechanisms outperform the existing solutions. Copyright © 2015 John Wiley & Sons, Ltd.
On energy‐efficient performance‐guaranteed channel assignment in cognitive radio‐based wireless mesh networks
Authors: ul Hasan Najam , Tu Wanqing
Published: June 2015

In recent years, in order to make efficient use of spectrum resources, much attention has been given to solving the problem of channel assignment in cognitive radio‐based wireless mesh networks (CR‐WMNs). Current approaches focus mainly on avoiding interference in order to enhance performance in terms of throughput. WMNs are intended to provide low‐cost multimedia communication. Therefore, in order to provide low‐cost real‐time communication, channel assignment in CR‐WMNs should take into consideration not only the issue of throughput, but also energy consumption and delays. In this paper, we first define an optimization problem to maximize the end‐to‐end throughput per unit of energy consumption while minimizing, as well as guaranteeing, the delay constraint specified for a data stream. Based on this, we then propose a novel distributive heuristic channel assignment approach to solve the optimization problem in a self‐organized manner. Finally, we present the simulation results to evaluate the performance of the proposed solution in terms of end‐to‐end throughput per unit of energy consumption and delays. Copyright © 2015 John Wiley & Sons, Ltd.
Effects of Acute and Sustained Pain Manipulations on Performance in a Visual‐Signal Detection Task of Attention in Rats
Authors: Freitas Kelen C. , Hillhouse Todd M. , Leitl Michael D. , Negus Steve S.
Published: June 2015

Preclinical Research

Patients with pain often display cognitive impairment including deficits in attention. The visual‐signal detection task (VSDT) is a behavioral procedure for assessment of attention in rodents. Male Sprague Dawley rats were trained in a VSDT and tested with three different noxious stimuli: (i) intraperitoneal injection of lactic acid; (ii) intraplantar injection of formalin; and (iii) intraplantar injection of complete Freund's adjuvant (CFA). The muscarinic acetylcholine receptor antagonist, scopolamine was also tested as a positive control. Scopolamine (0.01–1.0 mg/kg) dose dependently reduced accuracy and increased response latencies during completed trials with higher scopolamine doses increasing omissions. Lactic acid (0.56–5.6% ip) also increased response latencies and omissions, although it failed to alter measures of response accuracy. Formalin produced a transient decrease in accuracy while also increasing both response latency and omissions. CFA failed to alter VSDT performance. Although VSDT effects were transient for formalin and absent for CFA, both treatments produced mechanical allodynia and paw edema for up to 7 days. These results support the potential for noxious stimuli to produce a pain‐related disruption of attention in rats. However, relatively strong noxious stimulation appears necessary to disrupt performance in this version of the VSDT. Drug Dev Res 76 : 194–203, 2015. © 2015 Wiley Periodicals, Inc.
Heart failure with preserved ejection fraction: uncertainties and dilemmas
Authors: Ferrari Roberto , Böhm Michael , Cleland John G.F. , Paulus Walter J.S. , Pieske Burkert , Rapezzi Claudio , Tavazzi Luigi
Published: June 2015

Many uncertainties surround the syndrome of heart failure with preserved ejection fraction (HFpEF), which was the topic reviewed in an Expert Meeting at the University of Ferrara. This concluded that the absence of clear diagnostic clinical criteria was the major barrier to progress. There was general agreement that symptoms or signs of heart failure, normal LVEF despite an elevated plasma concentration of natriuretic peptides, and signs of abnormal LV relaxation, LV filling, LV hypertrophy, or left atrial enlargement, or diastolic dysfunction supported the diagnosis. However, HFpEF, like all heart failure syndromes, is heterogeneous in aetiology and pathophysiology, rather than being a single disease. HFpEF may account for about half of all patients with heart failure. The classical risk factors for developing HFpEF include age and co‐morbidities, notably hypertension, atrial fibrillation, and the metabolic syndrome. When complicated by increasing congestion requiring hospital admission, the prognosis is poor; 30% or more of patients will die within 1 year (nearly two‐thirds die from cardiovascular causes). Patients with chronic stable symptoms have a much better prognosis. Despite many clinical trials, there is no solid evidence that any treatment alters the natural history of HFpEF. Several treatments have shown promising early results and are now being tested in substantial randomized clinical trials. Further basic research is required to better characterize the disease and accelerate progress. Our review highlights the many difficulties encountered in performing randomized clinical trials in HFpEF, often due to difficulties in characterizing HFpEF itself.
Synthesis of an Iridium Peroxido Complex and Its Reactivity Towards Brønsted Acids
Authors: Baumgarth Hanna , Braun Thomas , Braun Beatrice , Laubenstein Reik , Herrmann Roy
Published: June 2015

Treatment of the iridium(I) complex trans‐[Ir(4‐C5F4N)(CNtBu)(PiPr3)2] (2) with O2 or H2O2 gave the iridium(III) peroxido complex trans‐[Ir(4‐C5F4N)(O2)(CNtBu)(PiPr3)2] (3a). The peroxido complex 3a reacts with Brønsted acids to give the iridium(III) complexes cis‐[Ir(4‐C5F4N)(X)2(CNtBu)(L)(PiPr3)] (4: X = Cl, L = PiPr3, 5: X = CF3COO, L = H2O) and hydrogen peroxide. In the presence of formic acid, 3a yields the carbonato complex trans‐[Ir{κ2‐OC(O)O}(4‐C5F4N)(CNtBu)(PiPr3)2] (6) as the main product. Reactions between formic acid or dihydrogen and the iridium(I) complex 2 give the isomeric dihydrido complexes trans,trans‐[Ir(4‐C5F4N)(H)2(CNtBu)(PiPr3)2] (7a) and cis,trans‐[Ir(4‐C5F4N)(H)2(CNtBu)(PiPr3)2] (9a), respectively.
Chemoselective Pd‐Catalyzed Isocyanide Insertion Reaction of Enaminones by C–H Functionalization: Hydrolysis or Cyclization through 1,3‐Palladium Migration
Authors: Gu Zheng‐Yang , Wang Xiang , Cao Jia‐Jia , Wang Shun‐Yi , Ji Shun‐Jun
Published: June 2015

A chemoselective palladium‐catalyzed isocyanide insertion reaction of enaminones was developed. Amide derivatives were synthesized by this C–H functionalization and subsequent hydrolysis reactions. 4‐Aminoquinoline derivatives were prepared by this C–H functionalization, which includes a 1,3‐palladium migration in the process.
Silver‐Catalyzed Aerobic Oxidative Decarboxylative Coupling of Arylpropiolic Acids with H‐Phosphine Oxides: Mild and Facile Synthesis of β‐Oxophosphine Oxides
Authors: Zeng Yao‐Fu , Tan Dong‐Hang , Lv Wen‐Xin , Li Qingjiang , Wang Honggen
Published: June 2015

A silver‐catalyzed oxidative decarboxylative coupling reaction of arylpropiolic acids with H‐phosphine oxides by using air as the terminal oxidant was developed. The reaction proceeds smoothly under mild conditions to give β‐oxophosphine oxides in moderate to good yields. Preliminary mechanistic studies were conducted.
Assessment of the Antioxidant Capacity of Standard Compounds and Fruit Juices by a Newly Developed Electrochemical Method: Comparative Study with Results from Other Analytical Methods
Authors: Gualandi Isacco , Ferraro Luca , Matteucci Pietro , Tonelli Domenica
Published: June 2015

The antioxidant capacity (AOC) of some standard compounds and commercial beverages was determined using an electroanalytical method which measures the OH radical scavenging ability (OH‐RSC). It is based on the degradation of a thin polyphenol film electrodeposited on glassy carbon following the attack by OH radicals produced by hydrogen peroxide photolysis. The degradation is prevented in presence of increasing concentrations of antioxidants. The same samples were also analyzed by DPPH, ABTS, and ORAC assays. The OH‐RSC method provided AOC values highly correlated with those resulting from the application of ORAC assay for both juices (R=0.90) and standard antioxidants (R=0.96).
Challenges in Lithium‐Ion‐Battery Slurry Preparation and Potential of Modifying Electrode Structures by Different Mixing Processes
Authors: Wenzel Valentin , Nirschl Hermann , Nötzel Dorit
Published: June 2015

The importance and possibilities to modify the morphology by mixing and dispersing is often neglected or underestimated. This Review works out the different opportunities in slurry preparation, using the example of lithium‐ion battery (LiB) manufacturing. In this case, also reference is made to possible interactions that are partly described in literature. This contribution outlines three different particle structures and the corresponding process‐control variations. Based on SEM pictures, the variation in morphology is shown and the effects of resulting network structures, percolation, electric contacting, and ionic exchange is discussed.
Achieving High‐Performance Supercapacitors by Constructing Porous Zinc–Manganese Oxide Microstructures
Authors: Gao Yanping , Zheng Mingbo , Pang Huan
Published: June 2015

Porous zinc–manganese oxide (ZnMn2O4) microstructures are prepared by calcination using a precursor method, and the material is successfully applied as the supercapacitor electroactive materials in a three‐electrode cell. Due to the unique micro/nanostructure, the as‐prepared sample obtained under the calcination condition of 450 °C for 6 h achieved a high specific capacitance of 1093 F g−1. The electrode also exhibited high cycle stability for 5000 cycles.
Synthesis of Substituted N‐Formylaminomethylenediphosphonates and Their Derivatives
Authors: Prishchenko Andrey A. , Livantsov Mikhail V. , Novikova Olga P. , Livantsova Ludmila I. , Averochkin Gleb M. , Petrosyan Valery S.
Published: June 2015

The convenient methods for the synthesis of new trimethylsilyl esters of aminomethylenediphosphonic acids are elaborated. The new substituted N‐formylaminomethylenediphosphonates are obtained via the interaction of trimethylsilyl esters of methylenediphosphonic acids with a mixture of triethyl orthoformate and ethanol. Also boron trifluoride–diethyl etherate as an effective catalyst is used for the interaction of hydrochlorides of ethoxymethylene imines with diethyl trimethylsilyl phosphite. The corresponding aminomethylenediphosphonic acids are presented.
Free Medicines Thanks to Retirement: Impact of Coinsurance Exemption on Pharmaceutical Expenditures and Hospitalization Offsets in a national health service
Authors: Puig‐Junoy Jaume , García‐Gómez Pilar , Casado‐Marín David
Published: June 2015

This paper examines the impact of coinsurance exemption for prescription medicines applied to elderly individuals in Spain after retirement. We use a rich administrative dataset that links pharmaceutical consumption and hospital discharge records for the full population aged 58 to 65 years in January 2004 covered by the public insurer in a Spanish region, and we follow them until December 2006. We use a difference‐in‐differences strategy and exploit the eligibility age for Social Security to control for the endogeneity of the retirement decision. Our results show that this uniform exemption increases the consumption of prescription medicines on average by 17.5%, total pharmaceutical expenditure by 25% and the costs borne by the insurer by 60.4%, without evidence of any offset effect in the form of lower short term probability of hospitalization. The impact is concentrated among consumers of medicines for acute and other non‐chronic diseases whose previous coinsurance rate was 30% to 40%. Copyright © 2015 John Wiley & Sons, Ltd.
Understanding the biosynthesis of platelets‐derived extracellular vesicles
Authors: Antwi‐Baffour Samuel , Adjei Jonathan , Aryeh Claudia , Kyeremeh Ransford , Kyei Foster , Seidu Mahmood A.
Published: June 2015

Platelet‐derived extracellular vesicles (PEVs) are described as sub‐cellular vesicles released into circulation upon platelets shear stress, activation, injury, or apoptosis. They are considered as universal biomarkers in a wide range of physiological and pathological processes. They are of tremendous significance for the prediction, diagnosis, and observation of the therapeutic success of many diseases. Understanding their biosynthesis and therefore functional properties would contribute to a better understanding of the pathological mechanisms leading to various diseases in which their levels are raised and they are implicated. The review takes a critical look at the historical background of PEVs, their structural components, the mechanism of their formation, physiological, and exogenous stimuli inducing their release and their detection. It concludes by highlighting on the importance of undertaking in‐depth studies into PEVs biosynthesis and subsequently gaining a better understanding of their biological role in general.
Decreased expression of CD200R3 on mouse basophils as a novel marker for IgG1‐mediated anaphylaxis
Authors: Iwamoto Hiroshi , Matsubara Takeshi , Nakazato Yuki , Namba Kazuyoshi , Takeda Yasuhiro
Published: June 2015

IgE‐mediated mast cell activation is the trigger of anaphylaxis in humans, whereas it is known that not only IgE but also IgG can induce anaphylaxis in mice. In our preliminary experiments, the expression of a murine basophil identification marker, CD200R3, on antigen‐sensitized basophils decreased following specific antigen challenge. Interestingly, this decrease did not always correspond with increased expression of the IgE‐mediated basophil activation marker CD200R1. Since IgG as well as IgE plays a role in mouse anaphylaxis, we hypothesized that the observed decrease in CD200R3 on basophils was caused by IgG‐mediated cell activation. We attempted to establish whether CD200R3 is a marker of IgG‐mediated basophil activation and if its expression is correlated with anaphylaxis in a mouse model. Mouse basophils were stimulated via FcϵRs and/or FcγRs, and levels of CD200R1 and CD200R3 were analyzed by flow cytometry. Basophils derived from naive mice were challenged with a natural antigen, β‐lactoglobulin, after passive sensitization with anti‐β‐LG serum or IgG/IgG subclass‐depleted antiserum. Systemic anaphylaxis was induced by i.v. injection of anti‐FcγRIII/II monoclonal antibody, and CD200R3 expression on peripheral basophils was assessed. Stimulation via FcϵRs induced a significant increase in CD200R1 expression but had only a small effect on that of CD200R3. However, anti‐FcγRIII/II stimulation reduced CD200R3 expression markedly. In passive sensitization experiments, down‐regulation of CD200R3 induced by antigen challenge was strongly negated by the depletion of IgG or IgG1 from antiserum. Intravenous injection of anti‐FcγRIII/II induced CD200R3 down‐regulation on peripheral basophils, together with a drop in rectal temperature. Lowered CD200R3 expression on basophils is induced by IgG‐mediated stimulation via FcγRs. Use of CD200R1 and CD200R3 as activation markers enables the evaluation of murine basophil activation mediated by IgE and IgG, respectively.
Areca nut exposure increases secretion of tumor‐promoting cytokines in gingival fibroblasts that trigger DNA damage in oral keratinocytes
Authors: Illeperuma Rasika P. , Kim Do Kyeong , Park Young Jin , Son Hwa Kyung , Kim Jue Young , Kim Jinmi , Lee Doo Young , Kim Ki‐Yeol , Jung Da‐Woon , Tilakaratne Wanninayake M. , Kim Jin
Published: June 2015

Molecular crosstalk between cancer cells and fibroblasts has been an emerging hot issue in understanding carcinogenesis. As oral submucous fibrosis (OSF) is an inflammatory fibrotic disease that can potentially transform into squamous cell carcinoma, OSF has been considered to be an appropriate model for studying the role of fibroblasts during early stage carcinogenesis. In this sense, this study aims at investigating whether areca nut (AN)‐exposed fibroblasts cause DNA damage of epithelial cells. For this study, immortalized hNOF (hTERT‐hNOF) was used. We found that the levels of GRO‐α, IL‐6 and IL‐8 increased in AN‐exposed fibroblasts. Cytokine secretion was reduced by antioxidants in AN‐exposed fibroblasts. Increase in DNA double strand breaks (DSB) and 8‐oxoG FITC‐conjugate was observed in immortalized human oral keratinocytes (IHOK) after the treatment of cytokines or a conditioned medium derived from AN‐exposed fibroblasts. Cytokine expression and DNA damage were also detected in OSF tissues. The DNA damage was reduced by neutralizing cytokines or antioxidant treatment. Generation of reactive oxygen species (ROS) and DNA damage response, triggered by cytokines, were abolished when NADPH oxidase (NOX) 1 and 4 were silenced in IHOK, indicating that cytokine‐triggered DNA damage was caused by ROS generation through NOX1 and NOX4. Taken together, this study provided strong evidence that blocking ROS generation might be a rewarding approach for cancer prevention and intervention in OSF.
Sharp IV Bounds on Average Treatment Effects on the Treated and Other Populations Under Endogeneity and Noncompliance
Authors: Huber Martin , Laffers Lukas , Mellace Giovanni
Published: June 2015

In the presence of an endogenous binary treatment and a valid binary instrument, causal effects are point identified only for the subpopulation of compliers, given that the treatment is monotone in the instrument. With the exception of the entire population, causal inference for further subpopulations has been widely ignored in econometrics. We invoke treatment monotonicity and/or dominance assumptions to derive sharp bounds on the average treatment effects on the treated, as well as on other groups. Furthermore, we use our methods to assess the educational impact of a school voucher program in Colombia and discuss testable implications of our assumptions. Copyright © 2015 John Wiley & Sons, Ltd.