bluuebunny/crossref_metadata_2025 huggingface dataset:
Key Considerations for Sensing FeII and FeIII in Aqueous Media
Authors: Burdette Shawn C.
Published: July 2015

Recently Ghosh et al. reported on the fluorescent response of commercially available N‐(2‐aminoethyl)naphthalen‐1‐amine toward FeII, FeIII, and HgII (K. Ghosh, S. Rathi, P. Gupta, P. Vashisth, V. Pruthi, Eur. J. Inorg. Chem. 2015, 311). The authors conclude that metal binding to the diamine chelator leads to chelation‐induced quenching; however, the experimental protocols are incompatible with the aqueous chemistry of FeIII, which precludes this interpretation of the data.
Water‐Soluble Palladium(II) Sulfonated Thiosemicarbazone Complexes: Facile Synthesis and Preliminary Catalytic Studies in the Suzuki–Miyaura Cross‐Coupling Reaction in Water
Authors: Matsinha Leah C. , Mao Jincheng , Mapolie Selwyn F. , Smith Gregory S.
Published: July 2015

A series of mono‐ and binuclear sulfonated thiosemicarbazone PdII complexes have been synthesised and characterised using nuclear magnetic resonance spectroscopy, infrared spectroscopy, electrospray ionisation mass spectrometry and elemental analysis. The complexes display excellent water‐solubility at room temperature and in addition, 1H and 31P{1H} NMR spectroscopic experiments reveal that the mononuclear complex 4 is very stable in water at 70 °C. Consequently, preliminary catalytic experiments show the water‐soluble complexes to be efficient catalyst precursors in the Suzuki–Miyaura cross‐coupling reaction in water. No evidence of homo‐coupling was observed and the water‐soluble complexes demonstrated versatility in coupling substrates containing various functional groups.
The acyltransferase activity of lipase CAL‐A allows efficient fatty acid esters formation from plant oil even in an aqueous environment
Authors: Müller Janett , Sowa Miriam A. , Dörr Mark , Bornscheuer Uwe T.
Published: July 2015

The enzymatic synthesis of fatty acid esters (FAE) can be performed by lipases in reaction systems in the absence of bulk water. However, some lipases such as Candida antarctica lipase A (CAL‐A) have an acyltransferase activity, which enables FAE synthesis from natural oils and suitable alcohols even in the presence of water. The ability to generate these compounds in an aqueous system would be interesting for an industrial application, because this could lead to a more cost‐efficient and environmentally friendly process as the alcohol donor also serves as solvent. Using refined palm kernel oil (PKO) the CAL‐A‐catalyzed ester synthesis was studied with methanol or ethanol in the presence of 5–10% (w/w) water. Optimizing reaction parameters (e.g., temperature and water content) resulted in up to 95% ester formation after 24 h. In addition, methanol allowed higher ester formation than ethanol.

Practical applications: The enzymatic synthesis of fatty acid esters from plant oils using standard lipases is hampered by the fact that the presence of water leads to undesired formation of free fatty acids. The use of CAL‐A with its unique acyltransferase activity overcomes this limitation and hence makes the industrial scale synthesis of these esters more feasible. The identification of important parameters influencing the ester formation is crucial to establish such processes.

Optimization of reaction conditions leads to protocols suitable to use lipase CAL‐A in a water containing system for the synthesis of fatty acid methyl or ethyl esters in up to 95% concentration.
Pd‐Catalyzed Allylic Alkynylation of Allylic Acetates with Terminal Alkynes
Authors: Yang Qingjing , Zhou Yongyun , Chen Jingchao , He Xiaobo , Xu Jianbin , Kwong Fuk Yee , Fan Baomin
Published: July 2015

The first palladium‐catalyzed allylic alkynylation reaction of allylic acetates with terminal alkynes has been realized. By empolying AgOTf as a cooperative catalyst, 1,4‐enynes were synthesized in up to 98 % yield under mild conditions. Moreover, the possible asymmetric version of this allylic alkynylation reaction was demonstrated.
Chiral Squaramide‐Catalyzed Michael/­Alkylation Cascade Reaction for the Asymmetric Synthesis of Nitro‐Spirocyclopropanes
Authors: Zhao Bo‐Liang , Du Da‐Ming
Published: July 2015

A new diastereoselective and enantioselective cyclopropanation reaction has been developed by employing a Michael/alkylation cascade reaction between (E)‐3‐arylenechroman‐4‐one or (E)‐2‐arylideneindan‐1‐one derivatives and a bromonitroalkane with a chiral squaramide catalyst. This reaction constitutes a facile asymmetric synthesis for nitro‐spirocyclopropanes that have three adjacent stereogenic centers, including one quaternary center, in moderate to good yields (up to 90 %) with excellent enantio‐ [up to >99 % ee (enantiomeric excess)] and diastereoselectivities [up to >99:1 dr (diastereomeric ratio)].
An Efficient Stereoselective Total Synthesis of All Stereoisomers of the Antibiotic Thiamphenicol through Ruthenium‐Catalyzed Asymmetric Reduction by Dynamic Kinetic Resolution
Authors: Perez Marc , Echeverria Pierre‐Georges , Martinez‐Arripe Elsa , Ez Zoubir Mehdi , Touati Ridha , Zhang Zhaoguo , Genet Jean‐Pierre , Phansavath Phannarath , Ayad Tahar , Ratovelomanana‐Vidal Virginie
Published: July 2015

Thiamphenicol is a widely used antibiotic that exhibits activity against numerous Gram‐positive and Gram‐negative pathogens. Here, we describe the expedient synthesis of its four stereoisomers through a dynamic kinetic resolution that follows a ruthenium‐catalyzed asymmetric hydrogenation or a hydrogen transfer reaction as the key step.
Enzymatic Synergism in the Synthesis of β‐Keto Esters
Authors: Wiśniewska Catalina , Koszelewski Dominik , Zysk Małgorzata , Kłossowski Szymon , Żądło Anna , Brodzka Anna , Ostaszewski Ryszard
Published: July 2015

Reaction of alcohols with ethyl and tert‐butyl acetoacetate catalyzed by a combination of commercially available enzymes is shown to be a convenient method for the preparation of a range of acetoacetic acid derivatives. Systematic studies proved that the combination of two or more enzymes enhances the yield of the reaction. Application of the selected enzyme mixture for enzymatic transesterification of various β‐keto esters provided the respective products in excellent yields up to 96 % and quantitative within 24 and 48 hours, respectively. The presented methodology is simple and mild, and can be used to prepare acetoacetates from primary and secondary alcohols.
Water‐Soluble Maleimide‐Modified Gold Nanoparticles (AuNPs) as a Platform for Cycloaddition Reactions
Authors: Ghiassian Sara , Gobbo Pierangelo , Workentin Mark S.
Published: July 2015

Maleimide‐terminated triethylene glycol thiolate monolayer‐protected gold nanoparticles (Mal‐EG4‐AuNPs) with a core size of 2.5 ± 0.7 nm were prepared. Mal‐EG4‐AuNPs were modified in high yields via interfacial 1,3‐dipolar cycloaddition and Diels–Alder reactions with a variety of nitrones and dienes, respectively. The resulting cycloadduct‐modified AuNPs were characterized using 1H NMR spectroscopy and were verified by comparison of the spectra to those of the products of the model reactions with the same nitrones and dienes. TEM analysis showed that the reaction conditions did not affect the shape or size of the gold core, suggesting that this is an efficient methodology to modify small water soluble AuNPs under ambient pressure and biological temperature with high yields and a reasonable reaction time.
Synthesis of Building Blocks for Carbopeptoids and Their Triazole Isoster Assembly
Authors: Rjabovs Vitālijs , Ostrovskis Pāvels , Posevins Daniels , Kiseļovs Gļebs , Kumpiņš Viktors , Mishnev Anatoly , Turks Māris
Published: July 2015

Synthetic approaches to new N‐protected γ‐ and δ‐furanoid sugar amino acids (SAAs) or tetrahydrofuran amino acids were developed. SAAs have emerged as valuable building blocks for the syntheses of peptide mimetics, so‐called carbopeptoids. 3‐C‐Substituted 1,2‐O‐isopropylidene‐α‐D‐allofuranose derivatives were used as starting materials. The designed SAAs contain either cis‐ or trans‐oriented C(3)‐aminomethyl and C(4)‐ or C(5)‐carboxylic acid functional groups attached to the 1,2‐O‐isopropylidene furanoid core, thus providing different spatial arrangements. Short‐chain homooligomers derived from a γ‐SAA and from a δ‐SAA were synthesized as the initial step towards exploration of new carbopeptoids. The key intermediates of these SAA syntheses can easily be transformed into the corresponding molecules containing azide and terminal alkyne moieties and as such have potential for future use for the syntheses of 1,2,3‐triazole isosters of peptides.
A Single Lipase‐Catalysed One‐Pot Protocol Combining Aminolysis Resolution and Aza‐Michael Addition: An Easy and Efficient Way to Synthesise β‐Amino Acid Esters
Authors: Xu Fan , Wu Qiongsi , Chen Xiaoyang , Lin Xianfu , Wu Qi
Published: July 2015

A novel one‐pot protocol combining aza‐Michael addition and aminolysis resolution was developed to obtain chiral β‐amino acid esters with lipase B from Candida antarctica (CAL‐B) as the only catalyst. This method is conducted under mild reaction conditions and is very easy to handle. After a series of detailed optimization studies, ten racemic aromatic or aliphatic amines were subjected to this one‐pot procedure, and twelve chiral β‐amino acid esters and ten chiral amides were successfully synthesised with excellent ee values in theoretical yields. Scaled‐up procedures also worked without apparent reduction in reaction rate or enantioselectivity, which makes this method suitable for large‐scale production of chiral β‐amino acid esters.
Synthesis of (R)‐BINOL‐Derived (Cyclopentadienone)iron Complexes and Their Application in the Catalytic Asymmetric Hydrogenation of Ketones
Authors: Gajewski Piotr , Renom‐Carrasco Marc , Facchini Sofia Vailati , Pignataro Luca , Lefort Laurent , de Vries Johannes G. , Ferraccioli Raffaella , Piarulli Umberto , Gennari Cesare
Published: July 2015

A family of chiral (cyclopentadienone)iron complexes, featuring an (R)‐BINOL‐derived backbone, and their application in the asymmetric hydrogenation of ketones are described. The complexes differ from each other in the substituents at the 3,3′‐positions of the binaphthyl residue (H, OH, OR, OCOR, OSO2R) or at the 2,5‐positions of the cyclopentadienone ring [trimethylsilyl (TMS) or Ph]. Remarkably, eight precatalysts with different 3,3′‐binaphthyl substitution [(R)‐1c–1j] were synthesized from a common parent complex [(R)‐1b] through direct functional group interconversion reactions of the complexes. The 3,3′‐(bis)methoxy‐substituted precatalyst (R)‐1b gave the best catalytic performance, and its application scope was assessed in the hydrogenation of several ketones. The observed ee values (up to 77 %) are much higher than those previously reported for other chiral (cyclopentadienone)iron complexes.
Analysis of the anti‐allodynic effects of combination of a synthetic cannabinoid and a selective noradrenaline re‐uptake inhibitor in nerve injury‐induced neuropathic mice
Authors: Gunduz O. , Topuz R.D. , Karadag C.H. , Ulugol A.
Published: July 2015

Background

Combining drugs not only reduces specific adverse effects of each of the drug at a higher dose but also may lead to enhanced efficacy. Tapentadol is a recently discovered analgesic possessing μ‐opioid receptor agonism and noradrenaline re‐uptake inhibition in a single molecule. Taking into consideration, the pharmacological similarities between opioids and cannabinoids, we assumed that combination of cannabinoids with noradrenaline re‐uptake inhibitors might also be effective. We therefore aimed to determine whether combining 1:1, 1:3 and 3:1 fixed ratios of the synthetic cannabinoid WIN 55,212‐2 and the selective noradrenaline re‐uptake inhibitor maprotiline exert anti‐allodynic synergy on nerve‐injured neuropathic mice.

Methods

Partial tight ligation of the sciatic nerve was made in mice; on pre‐operative and post‐operative 15 days basal mechanical allodynia, cold allodynia and motor function were assessed using von Frey filaments, hot/cold plate and rota rod apparatus.

Results

Mechanical and cold allodynia developed in all groups on post‐operative 15 days. Development of cold allodynia was statistically significant in all groups (p < 0.05); therefore, cold allodynia was used in combination studies. As shown by isobolographic analysis, interactions of 1:1 and 3:1 ratios of WIN 55,212‐2:maprotiline combinations were supra‐additive, whereas 1:3 ratio was sub‐additive.

Conclusions

Overall, our data suggest that combination of a cannabinoid with a selective noradrenaline re‐uptake inhibitor may offer a beneficial treatment option for neuropathic pain.
Switchable Bioelectrocatalysis Controlled by pH Changes
Authors: Katz Evgeny , Fernández Víctor M. , Pita Marcos
Published: July 2015

Application of stimuli‐responsive materials, particularly based on pH‐sensitive monolayers and thin‐films, to switchable bioelectrocatalysis is briefly overviewed in the paper. The switchable systems are exemplified with amino‐functionalized self‐assembled monolayers, polyelectrolyte brushes and complex biomolecular assemblies organized on electrode surfaces and demonstrating different electrochemical properties depending on pH values. The pH variation was achieved in situ due to biocatalytic reactions, thus coupling switchable bioelectrocatalysis with enzyme‐catalyzed reaction cascades. Future developments leading to complex biomolecular systems with switchable and tunable bioelectronics properties are envisaged as the result of research in this area.
Solution or Gas Phase? Oxidation and Radical Formation in Electrospray Ionization Mass Spectrometry (ESI MS)
Authors: Iftikhar Imran , Brajter‐Toth Anna
Published: July 2015

The relationship between one‐electron (e−) oxidation processes and the formation of radical cations of endogenous and exogenous compounds in vivo is of considerable interest. This paper reports on the experiments that allow FTICR mass spectrometric (MS) detection of ion signals that are consistent with the formation of radical cations of caffeine (CA) and theophylline (TP) during electrospray ionization (ESI) in ESI FTICR MS and in on‐line electrochemistry (EC)/ESI FTICR MS in positive mode. Significantly, the signals of the radicals of CA•+ and TP•+can be enhanced by simple modifications of the operating conditions in ESI MS, facilitating investigations of radical formation and related reactions.
Construction of Modified Carbon Paste Electrode for Highly Sensitive Simultaneous Electrochemical Determination of Trace Amounts of Copper (II) and Cadmium (II)
Authors: Afkhami Abbas , Soltani‐Shahrivar Morteza , Ghaedi Hamed , Madrakian Tayyebeh
Published: July 2015

A chemically modified electrode was constructed for rapid, simple, accurate, selective and highly sensitive simultaneous determination of Cu(II) and Cd(II) using square wave anodic stripping voltammetry. The electrode was prepared by incorporation of SiO2 nanoparticles, coated with a newly synthesized Schiff base, in carbon paste electrode. The limit of detection was found to be 0.28 ng mL−1 and 0.54 ng mL−1 for Cu(II) and Cd(II), respectively. The proposed chemically modified electrode was used for the determination of copper and cadmium in several foodstuffs and water samples.
Sequential Voltammetric Determination of Uranium, Cadmium and Lead by Using the ex situ Bismuth Film Electrode: Application to Phosphate Fertilizers
Authors: Jost Cristiane L. , di Martos Lara M. , Ferraz Luis , do Nascimento Paulo Cícero
Published: July 2015

A sequential voltammetric procedure for the determination of uranium, cadmium and lead was investigated at an ex situ bismuth film electrode (BiFE). First, the adsorptive stripping voltammetry was applied to assay the U(VI)‐cupferron complex in the differential pulse mode (detection limit of 1.0 µg L−1, 200 s accumulation time). Through the manipulation of the same aliquot of the sample, efforts were made to quantify cadmium and lead by square wave anodic stripping voltammetry. Detection limits of 2.03 µg L−1 for Cd (II) and 2.43 µg L−1 for Pb (II) were calculated (100 s accumulation time). The methodology was successfully applied to phosphate fertilizer samples after open vessel wet decomposition (HNO3/H2O2). The following value ranges were evaluated: U (VI) 37.2–150 mg kg−1, Pb (II) 78.3–204 mg kg−1 and Cd (II) 44.1–71.6 mg kg−1. Validation was performed by using the standard reference materials SRM‐695 – phosphate fertilizer – and SRM‐1643e – water.
TiO2 Nanomaterials as Anode Materials for Lithium‐Ion Rechargeable Batteries
Authors: Yan Xiaodong , Wang Zhihui , He Min , Hou Zhaohui , Xia Ting , Liu Gao , Chen Xiaobo
Published: July 2015

With the increased focus on sustainable energy, Li‐ion rechargeable batteries are playing more important roles in energy storage and utilization. Owing to their high safety, low cost, and moderate capacity, titanium dioxide (TiO2) nanomaterials have been considered as promising alternative anode materials for Li‐ion rechargeable batteries. Here, we present a concise overview of past research efforts on TiO2 nanomaterials as anode materials for Li‐ion rechargeable batteries. We focus on research examples that illustrate the importance of the nanometer‐scale, shape, dimensionality, and morphology of the TiO2 nanomaterials to their electrochemical properties for Li‐ion storage. Representative examples are given for nanoparticles, nanowires, nanotubes, nanosheets, and three‐dimensional materials, as well as amorphous structures. Approaches to improve the performance of TiO2 nanomaterials such as carbon coating, bulk doping, self‐structural modification, and compositing are surveyed briefly. Progress in the use of TiO2 nanomaterials in full‐cell configurations is also reviewed. Finally, the challenges for the practical applications of TiO2 nanomaterials in Li‐ion rechargeable batteries are discussed briefly.
Investigation of K2CO3‐Catalyzed Pyrolysis and Steam Gasification of Coal Char
Authors: Zhu Huaili , Wang Ximing , Zhang Jingang , Yao Kui , Yu Guangsuo , Wang Xingjun
Published: July 2015

Pyrolysis and steam gasification experiments of coal char with and without K2CO3 were performed using a thermogravimetric analyzer to investigate the effect of catalyst loading method on gasification reactivity at different temperatures (650–800 °C), and an additional redox cycle experiment of catalyzed char‐steam gasification was conducted in a fixed‐bed reactor. The results showed that, at low temperature, the solution impregnation method had a larger effect on the gasification reactivity than the physical blending method; at temperatures above 700 °C, the differences of two methods diminished due to the high mobility of potassium. In catalytic pyrolysis, the release of CO and CO2 indicated that K2CO3 reacted with carbon. The redox cycle experiments suggest that the potassium reacted with carbon to produce intermediates of the form K2O2C, K2OC, and K2C. The K2C intermediate may help to explain the release of more H2 during the initial period of catalytic coal char–steam gasification.
Decamethylcyclopentasiloxane (D5) environmental sources, fate, transport, and routes of exposure
Authors: Mackay Donald , Cowan-Ellsberry Christina E. , Powell David E. , Woodburn Kent B. , Xu Shihe , Kozerski Gary E. , Kim Jaeshin
Published: July 2015

The environmental sources, fate, transport, and routes of exposure of decamethylcyclopentasiloxane (D5; CAS no. 541-02-6) are reviewed in the present study, with the objective of contributing to effective risk evaluation and assessment of this and related substances. The present review, which is part of a series of studies discussing aspects of an effective risk evaluation and assessment, was prompted in part by the findings of a Board of Review undertaken to comment on a decision by Environment Canada made in 2008 to subject D5 to regulation as a toxic substance. The present review focuses on the early stages of the assessment process and how information on D5's physical–chemical properties, uses, and fate in the environment can be integrated to give a quantitative description of fate and exposure that is consistent with available monitoring data. Emphasis is placed on long-range atmospheric transport and fate in water bodies receiving effluents from wastewater treatment plants (along with associated sediments) and soils receiving biosolids. The resulting exposure estimates form the basis for assessments of the resulting risk presented in other studies in this series. Recommendations are made for developing an improved process by which D5 and related substances can be evaluated effectively for risk to humans and the environment. Environ Toxicol Chem 2015;34:2689–2702. © 2015 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC
Fugacity and activity analysis of the bioaccumulation and environmental risks of decamethylcyclopentasiloxane (D5)
Authors: Gobas Frank A.P.C. , Xu Shihe , Kozerski Gary , Powell David E. , Woodburn Kent B. , Mackay Don , Fairbrother Anne
Published: July 2015

As part of an initiative to evaluate commercial chemicals for their effects on human and environmental health, Canada recently evaluated decamethylcyclopentasiloxane (D5; CAS no. 541-02-06), a high–volume production chemical used in many personal care products. The evaluation illustrated the challenges encountered in environmental risk assessments and the need for the development of better tools to increase the weight of evidence in environmental risk assessments. The present study presents a new risk analysis method that applies thermodynamic principles of fugacity and activity to express the results of field monitoring and laboratory bioaccumulation and toxicity studies in a comprehensive risk analysis that can support risk assessments. Fugacity and activity ratios of D5 derived from bioaccumulation measures indicate that D5 does not biomagnify in food webs, likely because of biotransformation. The fugacity and activity analysis further demonstrates that reported no-observed-effect concentrations of D5 normally cannot occur in the environment. Observed fugacities and activities in the environment are, without exception, far below those corresponding with no observed effects, in many cases by several orders of magnitude. This analysis supports the conclusion of the Canadian Board of Review and the Minister of the Environment that D5 does not pose a danger to the environment. The present study further illustrates some of the limitations of a persistence-bioaccumulation-toxicity–type criteria-based risk assessment approach and discusses the merits of the fugacity and activity approach to increase the weight of evidence and consistency in environmental risk assessments of commercial chemicals. Environ Toxicol Chem 2015;34:2723–2731. © 2015 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.
Characterization of ecological risks from environmental releases of decamethylcyclopentasiloxane (D5)
Authors: Fairbrother Anne , Burton G. Allen , Klaine Stephen J. , Powell David E. , Staples Charles A. , Mihaich Ellen M. , Woodburn Kent B. , Gobas Frank A.P.C.
Published: July 2015

Decamethylcyclopentasiloxane (D5) is used in personal care products and industrial applications. The authors summarize the risks to the environment from D5 based on multiple lines of evidence and conclude that it presents negligible risk. Laboratory and field studies show that D5 is not toxic to aquatic organisms or benthic invertebrates up to its solubility limit in water or porewater or its sorptive capacity in sediment. Comparison of lipid-normalized internal concentrations with measured concentrations in benthos indicates that field-collected organisms do not achieve toxic levels of D5 in their tissues, suggesting negligible risk. Exposure to D5 resulted in a slight reduction of root biomass in barley at test concentrations 2 orders of magnitude greater than measured D5 levels in biosolids-amended soils and more than twice as high as the maximum calculated sorptive capacity of the soil. No effects were observed in soil invertebrates exposed to similar concentrations, indicating that D5 poses a de minimis risk to the terrestrial environment. High rates of metabolism and elimination of D5 compared with uptake rates from food results in biodilution in the food web rather than biomagnification, culminating in de minimis risk to higher trophic level organisms via the food chain. A fugacity approach substantiates all conclusions that were made on a concentration basis. Environ Toxicol Chem 2015;34:2715–2722. © 2015 SETAC
Synthesis, Stabilization and Activation of Pt Nanoparticles for PEMFC Applications
Authors: Latsuzbaia R. , Negro E. , Koper G.
Published: July 2015

Amongst the main challenges of catalyst materials for Proton Exchange Membrane Fuel Cells (PEMFCs) are activity and durability. Here we report on the synthesis of monodisperse nanoparticles and stabilization with traces of the surfactant, here Na‐AOT (bis‐(2‐ethylhexyl) sulfosuccinate sodium salt), used in the synthesis procedure. The surfactants prevent agglomeration and reduce Ostwald ripening. We compare the performance of Pt catalyst nanoparticles synthesized in dense microemulsions, Na‐AOT/heptane/water and Triton X‐100/toluene/water, with a commercial state‐of‐the‐art catalyst for the Oxygen Reduction Reaction (ORR). The produced catalyst nanoparticles were extracted onto a carbon support, Vulcan XC‐72R, washed and activated by heat‐treatment, which led to heavy agglomeration, or by electrochemical treatment, which led to an enhanced activity for ORR. Additionally, in comparison to the other two catalysts an increased durability of the platinum nanoparticles synthesized in the microemulsion of Na‐AOT/heptane/water was observed.
New Octopus‐like Phthalocyanines as Fullerene Receptors: Synthesis and Photophysical Investigation
Authors: Nefedova Irina V. , Martynov Alexander G. , Averin Alexey A. , Kirakosyan Gayane A. , Tsivadze Aslan Yu. , Gorbunova Yulia G.
Published: July 2015

Octopus‐like zinc and magnesium phthalocyaninates bearing eight flexible benzylated diethylene glycol chains were synthesized and their interaction with fullerenes C60 and C70 was investigated by UV‐Vis spectrophotometric titration, as well as by steady‐state and time‐resolved fluorescence spectroscopy in chloroform and toluene media. These measurements revealed a high affinity of receptors for C60 and C70, with selectivity to C70: binding constants for C70 are almost two times higher than for C60. These results are interpreted by means of quantum‐chemical calculations using the PM6‐DH2 Hamiltonian. The binding constants also depend on both the nature of the metal ion in the receptor and the solvent. It is expected that the obtained molecules and supramolecular complexes can be used for further elaboration of optoelectronic donor‐acceptor materials.
Longitudinal trajectories of bicultural identity integration in recently immigrated Hispanic adolescents: Links with mental health and family functioning
Authors: Schwartz Seth J. , Unger Jennifer B. , Baezconde‐Garbanati Lourdes , Benet‐Martínez Verónica , Meca Alan , Zamboanga Byron L. , Lorenzo‐Blanco Elma I. , Rosiers Sabrina E. Des , Oshri Assaf , Sabet Raha F. , Soto Daniel W. , Pattarroyo Monica , Huang Shi , Villamar Juan A. , Lizzi Karina M. , Szapocznik José
Published: July 2015

This study examined, in a sample of recently immigrated Hispanic adolescents in Miami and Los Angeles, the extent to which bicultural identity integration (BII; involving the ability to synthesise one's heritage and receiving cultural streams and to identify as a member of both cultures) is best understood as a developmental construct that changes over time or as an individual‐difference construct that is largely stable over time. We were also interested in the extent to which these trajectories predicted mental health and family functioning. Recent‐immigrant 9th graders (N = 302) were assessed 6 times from 9th to 12th grade. Latent class growth analyses using the first 5 timepoints identified 2 trajectory classes—one with lower BII scores over time and another with higher BII scores over time. Higher heritage and US identity at baseline predicted membership in the higher BII class. At the 6th study timepoint, lower BII adolescents reported significantly poorer self‐esteem, optimism, prosocial behaviour and family relationships compared with their higher BII counterparts. These findings are discussed in terms of further research on the over‐time trajectory of biculturalism, and on the need to develop interventions to promote BII as a way of facilitating well‐being and positive family functioning.
BDE‐209 inhibits pluripotent genes expression and induces apoptosis in human embryonic stem cells
Authors: Du Lili , Sun Wen , Zhang Huili , Chen Dunjin
Published: July 2015

Decabromodiphenyl ether (BDE‐209) has been detected in human serum, semen, placenta, cord blood and milk worldwide. However, little is known regarding the potential effects on the early human embryonic development of BDE‐209. In this study, human embryonic stem cell lines FY‐hES‐10 and FY‐hES‐26 were used to evaluate the potential effects and explore the toxification mechanisms using low‐level BDE‐209 exposure. Our data showed that BDE‐209 exposure (1, 10 and 100 nM) reduced the expression of pluripotent genes such as OCT4, SOX2 and NANOG and induced human embryonic stem cells (hESCs) apoptosis. The downregulation of BIRC5/BCL2 and upregulation of BAX were related to apoptosis of hESCs induced by BDE‐209 exposure. A mechanism study showed that OCT4 down‐regulation accompanied by OCT4 promoter hypermethylation and increasing miR‐145/miR‐335 levels, OCT4 inhibitors. Moreover, BDE‐209 could increase the generation of intracellular reactive oxygen species (ROS) and decrease SOD2 expression. The ROS increase and OCT4 downregulation after BDE‐209 exposure could be reversed partly by antioxidant N‐acetylcysteine supplement. These findings showed that BDE‐209 exposure could decrease pluripotent genes expression via epigenetic regulation and induce apoptosis through ROS generation in human embryonic stem cells in vitro. Copyright © 2015 John Wiley & Sons, Ltd.
Strain in nonclassical silicon hydrides: An insight into the “ultrastability” of sila‐bi[6]prismane (Si18H12) cluster with the endohedrally trapped silicon atom, Si19H12
Authors: Dolgonos Grygoriy A. , Mekalka Koshka
Published: July 2015

The recently postulated concept of “ultrastability” and “electron‐deficient aromaticity” (Vach, Nano Lett 2011, 11, 5477; Vach, J Chem Theory Comput 2012, 8, 2088) in a sila‐bi[6]prismane having an additional entrapped silicon atom, Si19H12, has been disproved on the basis of a careful analysis of the energetic characteristics related to the formation of this and other silicon hydrides. The central silicon atom in Si19H12 is weaker bound to other silicon atoms than in conventional tetrahedral silanes; moreover, Si19H12 possesses a significant amount of strain. The role of strain in the formation of the title compounds has been further rationalized by calculating the relative energies for the transformation to a half‐planar conformation in methane and in silane and by calculating the respective strain energies. The strain energy value in Si18H12 is equal to 9.93 eV whereas the same property for Si19H12 lies in range of 6.42–8.85 eV. Two low‐energy isomers of Si19H12 which lie by 2.77 and 3.42 eV (!) lower in energy than the originally considered sila‐bi[6]prismane‐based structure have been proposed. © 2015 Wiley Periodicals, Inc.
Potent immunotherapy against well‐established thymoma using adoptively transferred transgene IL‐6‐engineered dendritic cell‐stimulated CD8+ T‐cells with prolonged survival and enhanced cytotoxicity
Authors: Kalyanasundaram Bhanumathy Kalpana , Zhang Bei , Xie Yufeng , Xu Aizhang , Tan Xin , Xiang Jim
Published: July 2015

Background

Adoptive transfer of CD8+ T‐cells specific for tumor‐antigens is an attractive strategy for anti‐tumor therapy. In the present study, the subsets TA and TB were used to represent the population of CD8+ T cells generated by culturing the respective cells with irradiated dendritic cells (DCs) pulsed with ovalbumin (OVA) protein and transfected with adenoviral vector constructs as described.

Methods

Naïve OVA specific CD8+ T cells were isolated from the spleen of OVA‐specific T‐cell receptor transgenic OTI mice. The subsets TA and TB were then generated by in vitro activating the population of CD8+ T cells with OVA‐pulsed DCs transfected with IL‐6‐expressing adenoviral vector (AdVIL‐6) or the control vector (AdVNull). To assess their in vivo immunotherapeutic effects, TA‐ or TB‐cells were intravenously transferred into C57BL/6 mice bearing EG7 thymoma (6–8 mm in diameter).

Results

TA‐cells displayed a higher level of expression of CD62 l, IL‐7R, FasL, perforin and CCR6, and also exhibited more potent in vitro cytotoxicity to OVA‐expressing EG7 thymoma cells via perforin‐ and Fas/FasL‐mediated apoptosis than TB‐cells. CD8+ T‐cell survival was kinetically analyzed in C57BL/6 mice transferred with TA‐ or TB‐cells by flow cytometry. We found that the adoptively transferred TA‐cells had prolonged survival and enhanced T‐cell memory development compared to TB‐cells. In addition, TA‐, but not TB‐cells were able to eradicate well‐established EG7 thymomas in all eight tumor‐bearing mice.

Conclusions

Our data suggest that AdVIL‐6‐transfected DC‐stimulated CD8+ T cells with potent cytotoxicity and survival advantage may serve as an effective adoptive CD8+ T‐cell immunotherapy strategy for anti‐tumor treatment. Copyright © 2015 John Wiley & Sons, Ltd.
4D flow MRI can detect subtle right ventricular dysfunction in primary left ventricular disease
Authors: Fredriksson Alexandru Grigorescu , Svalbring Emil , Eriksson Jonatan , Dyverfeldt Petter , Alehagen Urban , Engvall Jan , Ebbers Tino , Carlhäll Carl‐Johan
Published: July 2015

Purpose

To investigate whether 4D flow magnetic resonance imaging (MRI) can detect subtle right ventricular (RV) dysfunction in primary left ventricular (LV) disease.

Materials and Methods

4D flow and morphological 3T MRI data were acquired in 22 patients with mild ischemic heart disease who were stratified into two groups based on LV end‐diastolic volume index (EDVI): lower‐LVEDVI and higher‐LVEDVI, as well as in 11 healthy controls. The RV volume was segmented at end‐diastole (ED) and end‐systole (ES). Pathlines were emitted from the ED volume and traced forwards and backwards in time to ES. The blood volume was separated into flow components. The Direct Flow (DF) component was defined as RV inflow passing directly to outflow. The kinetic energy (KE) of the DF component was calculated. Echocardiographic conventional RV indices were also assessed.

Results

The higher‐LVEDVI group had larger LVEDVI and lower LV ejection fraction (98 ± 32 ml/m2; 48 ± 13%) compared to the healthy (67 ± 12, P = 0.002; 64 ± 7, P < 0.001) and lower‐LVEDI groups (62 ± 10; 68 ± 7, both P < 0.001). The RV 4D flow‐specific measures “DF/EDV volume‐ratio” and “DF/EDV KE‐ratio at ED” were lower in the higher‐LVEDVI group (38 ± 5%; 52 ± 6%) compared to the healthy (44 ± 6; 65 ± 7, P = 0.018 and P < 0.001) and lower‐LVEDVI groups (44 ± 6; 64 ± 7, P = 0.011 and P < 0.001). There was no difference in any of the conventional MRI and echocardiographic RV indices between the three groups.

Conclusion

We found that in primary LV disease mild impairment of RV function can be detected by 4D flow‐specific measures, but not by the conventional MRI and echocardiographic indices. J. MAGN. RESON. IMAGING 2016;43:558–565.
Rhizosphere effects on Cu availability and fractionation in sewage sludge‐amended calcareous soils
Authors: Motaghian Hamid Reza , Hosseinpur Ali Reza
Published: July 2015

Rhizosphere processes have a major impact on copper (Cu) availability and its fractions in soils. A greenhouse experiment with wheat was performed to investigate availability (using seven chemical procedures) and fractionation of Cu in the rhizosphere of ten agricultural soils (Typic Calcixerepts) amended with sewage sludge (1% w/w) using rhizoboxes. The results show that available Cu concentrations in rhizosphere soils were significantly (P < 1%) lower than in bulk soils. In comparison with the bulk soils, in the rhizosphere soils the concentration of Cu associated with organic matter and residual Cu increased by 24 and 4%, respectively, whereas exchangeable Cu, Cu associated with iron‐manganese oxides, and Cu associated with carbonate decreased by 20, 14, and 12%, respectively. Dissolved organic carbon (DOC) and Cu associated with iron‐manganese oxides and Cu associated with organic matter in the rhizosphere and bulk soils were significantly correlated (P < 5%). The results show that the differences between rhizosphere and bulk soils in chemical conditions such as DOC concentrations can change the proportion of soil Cu fractions and, therefore, Cu availability for wheat in calcareous soils amended with sewage sludge. The results show that the wheat root‐induced modifications of chemical and biological soil conditions do not only lead to Cu depletion in mobile soil Cu fractions, but also to modification in soil Cu fractions which are commonly considered as more stable.
Effects of temperature on the quality of black garlic
Authors: Zhang Xinyan , Li Ningyang , Lu Xiaoming , Liu Pengli , Qiao Xuguang
Published: July 2015

BACKGROUND

Black garlic is a type of garlic product that is generally produced by heating raw garlic at high temperature with controlled humidity for more than 30 days. Black garlic has appeared on the market for many years. It is crucial to investigate the characteristics of quality formation of black garlic during processing at various temperatures.

RESULTS

In this study, fresh garlic was processed to black garlic at temperatures of 60, 70, 80 and 90 °C. Moisture, amino acid nitrogen and allicin contents decreased gradually during thermal processing of various temperatures. Reducing sugar, 5‐hydroxymethylfurfural, total phenols, total acids contents and browning increased. The changing rate of quality indicators and flavour of black garlic varied at different temperatures. Browning intensity reached about 74 when black garlic aged. The sensory score was significantly higher in black garlic aged at 70 °C (39.95 ± 0.31) compared with that at other temperatures, suggesting that 70 °C might facilitate formation of good quality and flavour of black garlic during processing.

CONCLUSION

Temperature had a remarkable impact on the quality and flavour of black garlic. © 2015 Society of Chemical Industry
A Process View to Evaluate and Understand Preference Elicitation
Authors: Nikou Shahrokh , Mezei József , Sarlin Peter
Published: July 2015

This paper focuses on multi‐attribute design problems in which several quantitative and/or qualitative attributes are simultaneously involved. Preference elicitation methods dealing with decision‐makers' preferences are often employed to solve such problems. The present paper proposes a conceptual framework that considers preference elicitation as a process shaped by the interaction of different factors including the researcher, methodology, questionnaire and respondent in a given context, at the same time. The aim of the framework is to assist in choosing a decision support tool among various multi‐attribute decision‐making methods, as well as in evaluating and understanding preference elicitation results. To illustrate and exemplify the use of the framework, it is applied to a real‐world case of end user preferences of mobile service platforms. We make use of two methods that are suitable for such a setting: analytic hierarchy process and conjoint analysis. Albeit with considerable discrepancies, the results show that both methods provide insightful information on the principle. Nonetheless, to a large degree, these methods perform differently in the case of non‐complex tasks and unknowledgeable respondents, which the process view aids in evaluating and understanding. Copyright © 2015 John Wiley & Sons, Ltd.
Loss of Dopamine Transporter Binding and Clinical Symptoms in Dementia With Lewy Bodies
Authors: Siepel Françoise J. , Dalen Ingvild , Grüner Renate , Booij Jan , Brønnick Kolbjørn S. , Buter Tirza C. , Aarsland Dag
Published: July 2015

Background

Little is known about the underlying mechanisms of clinical symptoms in dementia with Lewy bodies. The aim of this study was to explore the association between loss of striatal dopamine transporter binding and symptoms in dementia with Lewy bodies.

Methods

Thirty‐five patients with dementia with Lewy bodies underwent single‐photon emission computerized tomography brain imaging with N‐ω‐fluoropropyl‐2β‐carbomethoxy‐3β‐(4‐iodophenyl)nortropane ([123I]FP‐CIT). Associations between striatal binding ratios and motor (UPDRS), psychiatric (Neuropsychiatric Inventory; [NPI]), and cognitive (Mini–Mental State Examination [MMSE] and neuropsychological tests) symptoms were assessed by linear regression analysis.

Results

The explorative analysis showed that the motor UPDRS was negatively associated with putamen dopamine transporter binding, whereas no association with striatal dopamine transporter binding was found for total NPI, hallucinations, apathy, depression, anxiety, and MMSE scores. However, in post‐hoc analysis, executive impairment was positively associated with dopamine transporter loss after adjustment of age and gender.

Conclusions

Dopamine deficiency in patients with dementia with Lewy bodies was associated with severity of motor symptoms, but did not correlate significantly with ratings of neurobehavioral disturbances or overall cognition. © 2015 International Parkinson and Movement Disorder Society
Probable RBD and association with neurodegenerative disease markers: A population‐based study
Authors: Mahlknecht Philipp , Seppi Klaus , Frauscher Birgit , Kiechl Stefan , Willeit Johann , Stockner Heike , Djamshidian Atbin , Nocker Michael , Rastner Verena , Defrancesco Michaela , Rungger Gregor , Gasperi Arno , Poewe Werner , Högl Birgit
Published: July 2015

Background

The prevalence of rapid eye movement sleep behavior disorder (RBD) and its association with markers of neurodegeneration in the general population are poorly defined.

Methods

We assessed the prevalence of probable RBD defined by two validated questionnaires, the RBD Screening Questionnaire (RBDSQ) and the Innsbruck RBD‐Inventory (RBD‐I), and studied its associations with clinical and imaging markers for neurodegeneration in the Bruneck Study cohort aged 60 y or older.

Results

Of the 456 participants without Parkinson's disease, 4.6% (RBDSQ; 95%CI, 3.0%‐7.0%) and 7.7% (RBD‐I; 95%CI, 5.6%‐10.5%) had probable RBD. Probable RBD diagnosed with either of the questionnaires was associated with hyposmia (trend; P < 0.1), anxiety (P < 0.05), depression (P < 0.05), antidepressant use (P < 0.05), and self‐reported non‐motor symptoms (P < 0.01), specifically, dribbling saliva, memory problems, apathy, concentration problems, and anxiety.

Conclusions

Our findings may provide a basis for future studies intending to identify cohorts at risk for Lewy body diseases through screening of the general elderly population for RBD. © 2015 International Parkinson and Movement Disorder Society
The Evolution of Digital Chemistry at Southampton
Authors: Bird Colin , Coles Simon J. , Frey Jeremy G.
Published: July 2015

In this paper we take a historical view of e‐Science and e‐Research developments within the Chemical Sciences at the University of Southampton, showing the development of several stages of the evolving data ecosystem as Chemistry moves into the digital age of the 21st Century. We cover our research on aspects of the representation of chemical information in the context of the world wide web (WWW) and its semantic enhancement (the Semantic Web) and illustrate this with the example of the representation of quantities and units within the Semantic Web. We explore the changing nature of laboratories as computing power becomes increasing powerful and pervasive and specifically look at the function and role of electronic or digital notebooks. Having focussed on the creation of chemical data and information in context, we finish the paper by following the use and reuse of this data as facilitated by the features provided by digital repositories and their importance in facilitating the exchange of chemical information touching on the issues of open and or intelligent access to the data.
Dual‐polarity GRAPPA for simultaneous reconstruction and ghost correction of echo planar imaging data
Authors: Hoge W. Scott , Polimeni Jonathan R.
Published: July 2015

Purpose

The purpose of this study was to seek improved image quality from accelerated echo planar imaging (EPI) data, particularly at ultrahigh fields. Certain artifacts in EPI reconstructions can be attributed to nonlinear phase differences between data acquired using frequency‐encoding gradients of alternating polarity. These errors appear near regions of local susceptibility gradients and typically cannot be corrected with conventional Nyquist ghost correction (NGC) methods.

Methods

We propose a new reconstruction method that integrates ghost correction into the parallel imaging data recovery process. This is achieved through a pair of generalized autocalibrating partially parallel acquisitions (GRAPPA) kernels that operate directly on the measured EPI data. The proposed dual‐polarity GRAPPA (DPG) method estimates missing k‐space data while simultaneously correcting inherent EPI phase errors.

Results

Simulation results showed that standard NGC is incapable of correcting higher‐order phase errors, whereas the DPG kernel approach successfully removed these errors. The presence of higher‐order phase errors near regions of local susceptibility gradients was demonstrated with in vivo data. DPG reconstructions of in vivo 3T and 7T EPI data acquired near these regions showed a marked improvement over conventional methods.

Conclusion

This new parallel imaging method for reconstructing accelerated EPI data shows better resilience to inherent EPI phase errors, resulting in higher image quality in regions where higher‐order EPI phase errors commonly occur. Magn Reson Med 76:32–44, 2016. © 2015 Wiley Periodicals, Inc.
Hydrodistension with or without fulguration of hunner lesions for interstitial cystitis: Long‐term outcomes and prognostic predictors
Authors: Niimi Aya , Nomiya Akira , Yamada Yukio , Suzuki Motofumi , Fujimura Tetsuya , Fukuhara Hiroshi , Kume Haruki , Igawa Yasuhiko , Homma Yukio
Published: July 2015

Aims

Hydrodistension of the bladder, with optional fulguration of Hunner lesions, is one of the recommended therapies for interstitial cystitis (IC). The aims of this study are to evaluate long‐term outcomes of hydrodistension and identify outcome predictors.

Methods

The study cohort was 191 newly diagnosed IC patients (155 women and 36 men) who underwent hydrodistension with fulguration of Hunner lesions if detected between 2007 and 2013 at our institution. The primary outcome was therapeutic failure, which was defined as repeat hydrodistension, bladder instillation therapy, or narcotic use for pain control. Clinical features, including comorbidities and endoscopic findings, were analyzed along with the outcome.

Results

The cohort comprised 126 patients of Hunner type IC and 65 patients of non‐Hunner type IC. The mean time to therapeutic failure was 28.5 months in Hunner type IC and 25.2 months in non‐Hunner type IC. The therapeutic failure rate was higher in non‐Hunner type IC at 17.3 months; however, the long‐term outcomes reversed thereafter. The mean time to therapeutic failure was shorter in patients with lumbar spinal stenosis (LSS) or irritable bowel syndrome (IBS). Multivariate analysis identified LSS as a predictor for failure in Hunner type IC and non‐Hunner type IC (HR = 18.8, P = 0.001; HR = 3.8, P = 0.028, respectively) and IBS in non‐Hunner type IC (HR = 18.0, P = 0.008).

Conclusions

Bladder hydrodistension, with fulguration of the Hunner lesions, improved IC symptoms. The outcome was worse in non‐Hunner type IC shortly after hydrodistension but eventually comparable across the two types. Concomitant LSS and IBS were predictors for poor outcome. Neurourol. Urodynam. 35:965–969, 2016. © 2015 Wiley Periodicals, Inc.