bluuebunny/crossref_metadata_2025 huggingface dataset:
Electrooxidation Combined with Ozonation in Hospital Laundry Effluents Treatment
Authors: Lutterbeck Carlos Alexandre , de Oliveira Schwaickhardt Rômulo , Straatmann Alexandre , Kist Lourdes Teresinha , Lobo Eduardo A. , Machado Ênio Leandro
Published: July 2013

In the present study, treatment tests were performed on effluents generated from a hospital laundry using electrooxidation (EO) processes. Global parameter analyses and toxicological analyses were conducted before and after each trial. The analytical characterization of the effluent fractions from the hospital laundry revealed variable toxicities ranging from slightly toxic for the composite sample and extremely toxic for the Wash stage. Another parameter related to refractoriness at different currents involved measuring the chemical oxygen demand/biochemical oxygen demand (COD/BOD5) ratio, and a maximum ratio of 34.72 was observed in effluents from the wash stage. Ozonation, EO processes with iron electrodes alone, and combined with ozonation (EO/O3 and EO + O3) were used for the treatment tests. The tests involving the EO process for 60 min with induced conductivity through the addition of NaCl exhibited the best performance. Considering the best performance in previous assays, only the electrochemical methods were evaluated with the toxicological analyses. The application of the three‐electrochemical methods provided detoxification levels that improved to moderately or slightly toxic. In one of the conditions, the effluent generated in the initial rinse of the linens improved from the condition of extremely toxic (12.58%) to moderately toxic (61.59%), while the COD decreased by 9%. With respect to the effluent coming from the wash step, the COD showed a 41% reduction, while the toxicity was reduced considerably from the condition of extremely toxic (6.89%) to slightly toxic (76.65%).
Biodegradation of a Paper and Pulp Effluent by Rhodococcus sp. NCIM 2891 and Its Toxicity Assessments
Authors: Nadaf Naiem H. , Ghosh Jai S.
Published: July 2013

This investigation is aimed to reduce the pollution and ecotoxicological impact of the paper and pulp industry effluent by Rhodococcus sp. NCIM 2891. It was observed that the Rhodococcus sp. NCIM 2891, when grown in the presence of the effluent, there was a significant decrease in levels of biological oxygen demand (81.25%) 30 mg/L and chemical oxygen demand (53.23%) 363 mg/L as compared to untreated samples with 160 and 776 mg/L, respectively. Reduction in total dissolved solids could be observed (81%) along with reduction in heavy metal concentration. Further analysis of the degraded effluent compounds was carried out by atomic absorption spectroscopy. The eco‐compatibility of the effluent and degraded product was checked in terms of their toxicity on Allium cepa, Acantopsis choirorhynchus, and different microorganisms. The degraded products obtained after biodegradation are found to be eco‐compatible and non‐toxic.
Quantification of Ionic Liquids Concentration in Water and Qualification of Conjugated and Inductive Effects of Ionic Liquids by UV Spectroscopy
Authors: Cao Yuanyuan , Chen Yu , Sun Xiaofu , Mu Tiancheng
Published: July 2013

The determination of the concentrations of ionic liquids (ILs) in water by UV spectroscopy was proposed. The effects of alkyl chain length, anion, cation, and C2 methylation of ILs were systematically investigated. The concentration detection limit ranges from 0.625 to 80 mg/L, and can be extended by changing the path length of the UV cuvette. In addition, the conjugated and inductive effects of ILs were analyzed by the maximum absorption wavelength λmax. Cations without conjugated effect (e.g., pyrrolidium, tetraammonium, and tetraphosphonium) show no UV spectra peak, while cations with conjugated effects (e.g., imidazolium, and pyridinium) present UV spectra peaks. Electron‐donating substitute groups (e.g., alkyl, C2 methylation) induce a larger value of maximum absorption wavelength λmax than the electron‐withdrawing substitute groups (e.g., amine, non‐C2 methylation). These findings are helpful to detect and quantify the concentration of ILs in water.
Glioblastoma survival in the United States improved after Food and Drug Administration approval of bevacizumab: A population‐based analysis
Authors: Johnson Derek R. , Leeper Heather E. , Uhm Joon H.
Published: July 2013

BACKGROUND

Bevacizumab received US Food and Drug Administration approval for use in recurrent glioblastoma based on promising radiographic response data, but without clear evidence that it prolongs survival. A population‐based analysis was conducted to determine whether bevacizumab approval was associated with improved glioblastoma survival in the United States.

METHODS

Surveillance, Epidemiology, and End Results (SEER) Program data were used to compare survival of glioblastoma patients who died in 2006, 2008 (both prior to approval of bevacizumab), and 2010 (after approval of bevacizumab).

RESULTS

The SEER database contained 1715 patients with glioblastoma who died in 2006, 1924 who died in 2008, and 1968 who died in 2010 who met study inclusion criteria. Median survival was 8 months for those who died in 2006, 7 months in 2008, and 9 months in 2010. The difference in survival between 2008 (pre‐bevacizumab) and 2010 (post‐bevacizumab) was highly significant. This difference is unlikely to be due to improvements in supportive care in this short interval, because there was no significant difference (P = .4440) between patients who died in 2006 versus those who died in 2008. Between 2008 and 2010, a statistically significant improvement in survival was seen in all age groups except those patients aged 18 to 39 years.

CONCLUSIONS

Patients who died of glioblastoma in 2010 had lived with disease significantly longer than patients who died in 2008. The most likely explanation for this change is the approval and use of bevacizumab for progressive glioblastoma, indicating that at a population level, treatment strategies involving bevacizumab prolong survival. Cancer 2013;119:3489–3495.. © 2013 American Cancer Society.
Numerical quadrature and operator splitting in finite element methods for cardiac electrophysiology
Authors: Krishnamoorthi Shankarjee , Sarkar Mainak , Klug William S.
Published: July 2013

We study the numerical accuracy and computational efficiency of alternative formulations of the finite element solution procedure for the monodomain equations of cardiac electrophysiology, focusing on the interaction of spatial quadrature implementations with operator splitting and examining both nodal and Gauss quadrature methods and implementations that mix nodal storage of state variables with Gauss quadrature. We evaluate the performance of all possible combinations of ‘lumped’ approximations of consistent capacitance and mass matrices. Most generally, we find that quadrature schemes and lumped approximations that produce decoupled nodal ionic equations allow for the greatest computational efficiency, this being afforded through the use of asynchronous adaptive time‐stepping of the ionic state variable ODEs. We identify two lumped approximation schemes that exhibit superior accuracy, rivaling that of the most expensive variationally consistent implementations. Finally, we illustrate some of the physiological consequences of discretization error in electrophysiological simulation relevant to cardiac arrhythmia and fibrillation. These results suggest caution with the use of semi‐automated free‐form tetrahedral and hexahedral meshing algorithms available in most commercially available meshing software, which produce nonuniform meshes having a large distribution of element sizes. Copyright © 2013 John Wiley & Sons, Ltd.
Modeling the dispersion in electromechanically coupled myocardium
Authors: Eriksson Thomas S. E. , Prassl Anton J. , Plank Gernot , Holzapfel Gerhard A.
Published: July 2013

We present an approach to model the dispersion of fiber and sheet orientations in the myocardium. By utilizing structure parameters, an existing orthotropic and invariant‐based constitutive model developed to describe the passive behavior of the myocardium is augmented. Two dispersion parameters are fitted to experimentally observed angular dispersion data of the myocardial tissue. Computations are performed on a unit myocardium tissue cube and on a slice of the left ventricle indicating that the dispersion parameter has an effect on the myocardial deformation and stress development. The use of fiber dispersions relating to a pathological myocardium had a rather big effect. The final example represents an ellipsoidal model of the left ventricle indicating the influence of fiber and sheet dispersions upon contraction over a cardiac cycle. Although only a minor shift in the pressure–volume (PV) loops between the cases with no dispersions and with fiber and sheet dispersions for a healthy myocardium was observed, a remarkably different behavior is obtained with a fiber dispersion relating to a diseased myocardium. In future simulations, this dispersion model for myocardial tissue may advantageously be used together with models of, for example, growth and remodeling of various cardiac diseases. Copyright © 2013 John Wiley & Sons, Ltd.
Influence of the Metal Ion on the Two‐Photon Absorption Properties of Lanthanide Complexes Including Near‐IR Emitters
Authors: Bourdolle Adrien , Allali Mustapha , D'Aléo Anthony , Baldeck Patrice L. , Kamada Kenji , Williams J. A. Gareth , Le Bozec Hubert , Andraud Chantal , Maury Olivier
Published: July 2013

The synthesis of tris(2‐thenoyltrifluoroacetonate)lanthanide(III) complexes featuring a diethylaminostyryl‐2,2′‐bipyridine coligand was achieved for lanthanum; the near‐infrared (NIR) emitters neodymium, erbium, and ytterbium; and the transition‐metal yttrium. The photophysical properties were thoroughly studied, and it was demonstrated that the conjugated bipyridine ligand acts as a good antenna for the sensitization of the NIR emitters. The two‐photon absorption (TPA) properties of all five complexes were investigated by using both two‐photon excited fluorescence and the Z‐scan method. We demonstrate that the nature of the rare earth ion has almost no influence on the TPA properties centered on the conjugated bipyridyl ligand. Finally, we show that YbIII is sensitized by a two‐photon antenna effect, and that NdIII is mostly sensitized by a one‐photon process involving direct excitation of forbidden f–f transitions.
Superhydrophobic Mesoporous Graphene for Separation and Absorption
Authors: Fan Zong‐Liang , Qin Xiao‐Juan , Sun Han‐Xue , Zhu Zhao‐Qi , Pei Chun‐juan , Liang Wei‐Dong , Bao Xue‐Mei , An Jin , La Pei‐Qing , Li An , Deng Wei‐Qiao
Published: July 2013

Mesoporous graphene with a surface area of 306 m2 g−1 was synthesized by employing CaCO3 microspheres as hard templates. By surface modification with polydimethylsiloxane (PDMS) through chemical vapor deposition, the wettability of as‐treated mesoporous graphene can be tailored to be superhydrophobic to water while superoleophilic to oils. The deposition of the low‐surface‐energy silicon‐coating originated from PDMS pyrolysis on porous graphene was confirmed by X‐ray photoelectron spectroscopy. As a result of its porous structures and excellent surface superhydrophobicity, the PDMS‐treated mesoporous graphene exhibits good selectivity, excellent recyclability, and good absorption performance (up to 66 g g−1) for a wide range of oils and organic solvents. Thus, leading to potential use in a variety of applications such as water treatment and purification as well as cleanup of oil spills.
Understanding Conflict Management Systems and Strategies in the Workplace: A Pilot Study
Authors: Katz Neil H. , Flynn Linda T.
Published: July 2013

In today's business environment, workplace conflict is a significant issue. Research in the conflict management discipline says that conflict in the workplace is on the rise and will continue to go up; however, many leaders and managers are not fully aware of structures and processes available to manage it. This article presents the results of a pilot study conducted in Broward County, Florida, of workplace leaders' and managers' awareness, perception, and use of conflict management systems and strategies. The findings reflect the lack of a clear definition of the issue, the absence of integrated conflict management systems within most organizations, and dissatisfaction with antiquated grievance systems. There is substantial opportunity for additional research.
A Pedagogy of Social Justice Education: Social Identity Theory, Intersectionality, and Empowerment
Authors: Hahn Tapper Aaron J.
Published: July 2013

This article explores a theoretical and practical understanding of social justice education through an examination of a US‐based intergroup educational organization running conflict transformation programs since 2005. Based on in‐depth interviews conducted with and surveys completed by administrators, educators, and student participants of the organization's programs, this article analyzes a case example of social justice education that integrates Freirean thought, social identity theory, intersectionality, and experiential education, including empowerment and responsibility education. Offering different programs aimed at distinct constituencies yet all based in the same pedagogy, the organization's primary goal is to empower participants to engage in social justice activism.
A Reflexive Approach to Risk and Intervention for Third‐Party Intervenors
Authors: Fast Larissa
Published: July 2013

In violent contexts, intervenors face dangers and are sometimes targets of violence themselves. Data and discussion about these risks and strategies to address them are missing from the peacebuilding literature. This article begins to address this gap. I argue that existing conflict analysis models provide a foundation for risk analysis, but they do not recognize the interplay between an organization's policies and intervention approaches and its security. I review two generations of conflict analysis frameworks and then present an approach that identifies various dimensions and types of risk and vulnerability for third‐party intervenors and integrates easily into existing analytical frameworks.
Whiter, Brighter, and More Stable Cellulose Paper Coated with TiO2/SiO2 Core/Shell Nanoparticles using a Layer‐by‐Layer Approach
Authors: Cheng Fei , Lorch Mark , Sajedin Seyed Mani , Kelly Stephen M. , Kornherr Andreas
Published: July 2013

To inhibit the photocatalytic degradation of organic material supports induced by small titania (TiO2) nanoparticles, four kinds of TiO2 nanoparticles, that is, commercial P25‐TiO2, commercial rutile phase TiO2, rutile TiO2 nanorods and rutile TiO2 spheres, prepared from TiCl4, were coated with a thin, but dense, coating of silica (SiO2) using a conventional sol–gel technique to form TiO2/SiO2 core/shell nanoparticles. These core/shell particles were deposited and fixed as a very thin coating onto the surface of cellulose paper samples by a wet‐chemistry polyelectrolyte layer‐by‐layer approach. The TiO2/SiO2 nanocoated paper samples exhibit higher whiteness and brightness and greater stability to UV‐bleaching than comparable samples of blank paper. There are many potential applications for this green chemistry approach to protect cellulosic fibres from UV‐bleaching in sunlight and to improve their whiteness and brightness.
Global unique solvability for memristive circuit DAEs of Index 1
Authors: Jansen Lennart , Matthes Michael , Tischendorf Caren
Published: July 2013

Known solvability results for nonlinear index‐1 differential‐algebraic equations (DAEs) are in general local and rely on the Implicit Function Theorem. In this paper, we derive a global result which guarantees unique solvability on a given time interval for a certain class of index‐1 DAEs with certain monotonicity conditions. Based on this result, we show that memristive circuit DAEs arising from the modified nodal analysis are uniquely solvable if they fulfill certain passivity and network topological conditions.

Furthermore we present an error estimation for the solution with respect to perturbations on the right‐hand side and in the initial value. Copyright © 2013 John Wiley & Sons, Ltd.
Cost reduction in bottom‐up hierarchical‐based VLSI floorplanning designs
Authors: Hoo Chyi‐Shiang , Jeevan Kanesan , Ramiah Harikrishnan
Published: July 2013

From the industrial perspective, floorplanning is a crucial step in the VLSI physical design process as its efficiency determines the quality and the time‐to‐market of the product. A new perturbation method, called Cull‐and‐Aggregate Bottom‐up Floorplanner (CABF), which consists of culling and aggregating stages, is developed to perform variable‐order automated floorplanning for VLSI. CABF will generate VLSI floorplan layout by calculating the modules' dimensions' differences (hard module floorplanning problems) and the modules' areas' differences (soft module floorplanning problems). Through mathematical derivation, the hard modules floorplanning area minimization cost function (two‐dimensional) during culling stage is proven that a dimensional reduction can be carried out to be the difference‐based cost function (one‐dimensional) which simplifies the computation. During the culling stage, CABF employs linear ordering method to select and determine the order of modules where this linear runtime complexity property allows CABF to cull the modules faster. The aggregating stage of CABF will reduce the subsequent search space of this floorplanner, and the variable order aggregation enables CABF to search for the best near‐optimal solution. Based on Gigascale Systems Research Center and Microelectronics Center of North Carolina circuit benchmarks, CABF gives better optimal solutions and faster runtimes for floorplanning problems involving 9 to 600 modules. This has established that CABF is performing well in respect of reliability and scalability. Besides, CABF shows its potential to be implemented in VLSI physical design as the runtime of CABF is faster with a near‐optimal outcome as compared to the other existing algorithms. Copyright © 2013 John Wiley & Sons, Ltd.
Rapid and simple LC‐MS/MS screening of 64 novel psychoactive substances using dried blood spots
Authors: Ambach Lars , Hernández Redondo Ana , König Stefan , Weinmann Wolfgang
Published: July 2013

The range of novel psychoactive substances (NPS) including phenethylamines, cathinones, piperazines, tryptamines, etc. is continuously growing. Therefore, fast and reliable screening methods for these compounds are essential and needed. The use of dried blood spots (DBS) for a fast straightforward approach helps to simplify and shorten sample preparation significantly. DBS were produced from 10 µl of whole blood and extracted offline with 500 µl methanol followed by evaporation and reconstitution in mobile phase. Reversed‐phase chromatographic separation and mass spectrometric detection (RP‐LC‐MS/MS) was achieved within a run time of 10 min. The screening method was validated by evaluating the following parameters: limit of detection (LOD), matrix effect, selectivity and specificity, extraction efficiency, and short‐term and long‐term stability. Furthermore, the method was applied to authentic samples and results were compared with those obtained with a validated whole blood method used for routine analysis of NPS. LOD was between 1 and 10 ng/ml. No interference from matrix compounds was observed. The method was proven to be specific and selective for the analytes, although with limitations for 3‐FMC/flephedrone and MDDMA/MDEA. Mean extraction efficiency was 84.6 %. All substances were stable in DBS for at least a week when cooled. Cooling was essential for the stability of cathinones. Prepared samples were stable for at least 3 days. Comparison to the validated whole blood method yielded similar results. DBS were shown to be useful in developing a rapid screening method for NPS with simplified sample preparation. Copyright © 2013 John Wiley & Sons, Ltd.
Variability of cannabis potency in the Venice area (Italy): A survey over the period 2010–2012
Authors: Zamengo Luca , Frison Giampietro , Bettin Chiara , Sciarrone Rocco
Published: July 2013

Cannabis is the most widely used illicit substance globally, with an estimated annual prevalence in 2010 of 2.6–5.0% of the adult population. Concerns have been expressed about increases in the potency of cannabis products. A high tetrahydrocannabinol (THC) content can increase anxiety, depression, and psychotic symptoms, and can increase the risk of dependence and adverse effects on the respiratory and cardiovascular systems in regular users. The aim of this study was to report statistical data about the potency of cannabis products seized in the north‐east of Italy, in a geographical area centred in Venice and extending for more than 10 000 km2 with a population of more than two million, by investigating the variability observed in THC levels of about 4000 samples of cannabis products analyzed over the period 2010–2012. Overall median THC content showed an increasing trend over the study period from about 6.0% to 8.1% (6.2–8.9% for cannabis resin, 5.1–7.6% for herbal cannabis). The variation in the THC content of individual samples was very large, ranging from 0.3% to 31% for cannabis resin and from 0.1 to 19% for herbal cannabis.

Median CBN:THC ratios showed a slightly decreasing trend over the study period, from 0.09 (2010) to 0.03 (2012), suggesting an increasing freshness of submitted materials. Median CBD:THC ratios also showed a decreasing trend over the study from about 0.52 (2010) to 0.18 (2012), likely due to the increase in submissions of materials from indoor and domestic cultivation with improved breeding methods. Copyright © 2013 John Wiley & Sons, Ltd.
Expanding analytical possibilities concerning the detection of stanozolol misuse by means of high resolution/high accuracy mass spectrometric detection of stanozolol glucuronides in human sports drug testing
Authors: Schänzer Wilhelm , Guddat Sven , Thomas Andreas , Opfermann Georg , Geyer Hans , Thevis Mario
Published: July 2013

Anabolic‐androgenic steroids (AAS) represent one of the most frequently detected classes of prohibited substances in doping controls. Due to their long‐lasting beneficial effects on athletic performance, utmost retrospectivity via urine analysis is desirable and accomplished by targeting long‐term metabolites of the respective drugs. In case of stanozolol, a substantial variety of metabolites has enabled the identification of numerous adverse analytical findings in the past, and recent studies concerning complementary phase‐I and phase‐II metabolites has further expanded the windows of opportunity for detecting the abuse of stanozolol. In this study, the utility of liquid chromatography‐high resolution/high accuracy (tandem) mass spectrometry (LC‐MS/MS) for the detection of 3’‐OH‐stanozolol glucuronide in sports drug testing is presented and the identification of two additional and so far unreported metabolites is shown. The structures of the complementary glucuronic acid conjugates were attributed to stanozolol‐N‐glucuronide and 17‐epistanozolol‐N‐glucuronide. By means of chemical synthesis, stanozolol‐N‐glucuronide was prepared and used to corroborate the suggested structures. The 3’‐OH‐stanozolol glucuronide and the newly identified target compounds were implemented into routine sports drug test assays consisting of direct injection LC‐MS/MS or solid‐phase extraction (SPE) followed by LC‐MS/MS. A considerably expanded detection window for stanozolol abuse was demonstrated compared to the use of conventional phase‐I metabolites and methodologies based on, for example, low resolution LC‐MS/MS or gas chromatography‐tandem mass spectrometry (GC‐MS/MS). The commercial availability of 3’‐OH‐stanozolol glucuronide has been of great value for confirmatory purposes, and 17‐epistanozolol‐N‐glucuronide was found to be a favourable long‐term metabolite for doping controls as it was observed up to 28 days post‐administration of the drug. Applying the established methodology over a period of six months to 659 routine sports drug testing samples, a total of 85 adverse analytical findings was uncovered, 72 of which would have remained undetected using earlier employed GC‐MS/MS approaches. Copyright © 2013 John Wiley & Sons, Ltd.
Biochemistry of the tale transcription factors PREP, MEIS, and PBX in vertebrates
Authors: Longobardi E. , Penkov D. , Mateos D. , De Florian G. , Torres M. , Blasi Francesco
Published: July 2013

TALE (three amino acids loop extension) homeodomain transcription factors are required in various steps of embryo development, in many adult physiological functions, and are involved in important pathologies. This review focuses on the PREP, MEIS, and PBX sub‐families of TALE factors and aims at giving information on their biochemical properties, i.e., structure, interactors, and interaction surfaces. Members of the three sets of protein form dimers in which the common partner is PBX but they can also directly interact with other proteins forming higher‐order complexes, in particular HOX. Finally, recent advances in determining the genome‐wide DNA‐binding sites of PREP1, MEIS1, and PBX1, and their partial correspondence with the binding sites of some HOX proteins, are reviewed. These studies have generated a few general rules that can be applied to all members of the three gene families. PREP and MEIS recognize slightly different consensus sequences: PREP prefers to bind to promoters and to have PBX as a DNA‐binding partner; MEIS prefers HOX as partner, and both PREP and MEIS drive PBX to their own binding sites. This outlines the clear individuality of the PREP and MEIS proteins, the former mostly devoted to basic cellular functions, the latter more to developmental functions. Developmental Dynamics 243:59–75, 2014. © 2013 Wiley Periodicals, Inc.
A PdII Complex Bearing a Benzimidazole‐Derived Ligand with Potentially “Mesoionic and Remote” Character and Its Catalytic Activity
Authors: Huynh Han Vinh , Ong Hong Lee , Bernhammer Jan C. , Frison Gilles
Published: July 2013

The oxidative addition of palladium(0) to the C2‐protected 5‐bromo‐2‐methylbenzimidazolium tetrafluoroborate 3 affords the complex trans‐[PdBr(bimy)(PPh3)2]BF4 (4), which is the first complex of an unprecedented benzimidazole‐derived ligand (bimy) with a potentially “mesoionic and remote” character. DFT calculations revealed that the bimy ligand bridges the gap between the mesoionic pyrazolin‐4‐ylidene and the anionic phenyl ligand. A preliminary catalytic study revealed the promising activity of 4 in the Sonogashira coupling of aryl bromides with phenylacetylene.
Diperoxo Pertechnetic Acid Characterized by Spectroscopic and Quantum Chemical Studies
Authors: Poineau Frederic , Weck Philippe F. , Burton‐Pye Benjamin P. , Kim Eunja , Francesconi Lynn C. , Sattelberger Alfred P. , German Konstantin E. , Czerwinski Kenneth R.
Published: July 2013

The reaction of Tc(+7) with H2O2 has been studied in HNO3 and the speciation of technetium was performed by UV/Vis spectroscopic analysis. UV/Vis measurements show that for HNO3 concentrations of more than 7 M and H2O2 concentrations of 4.25 M, Tc(+7) reacts immediately and red solutions are obtained, whereas no reaction occurs at H2O2 concentrations of 0.1 M. The UV/Vis spectra of the red solutions exhibit a single band centered at 500 nm that is attributed to a Tc(+7) peroxo species. The nature of the Tc(+7) peroxo species was investigated by computational methods. The structures and electronic spectra of the putative species Tc(O2)4–, TcO(O2)3–, TcO3(O2)–, TcO(O2)2(H2O)(OH), and TcO2(O2)(H2O)2(OH) were studied by first principles methods. Calculations show these species to be stable; their calculated spectra were compared to the experimental spectrum and the results are consistent with the presence of diperoxo pertechnetic acid, i.e., TcO(O2)2(H2O)(OH).
Unveiling the Interaction of Vanadium Compounds with Human Serum Albumin by Using 1H STD NMR and Computational Docking Studies
Authors: Dias David M. , Rodrigues João P. G. L. M. , Domingues Neuza S. , Bonvin Alexandre M. J. J. , Castro M. Margarida C. A.
Published: July 2013

The binding of the VV oxidation products of two vanadium(IV) compounds, [VO(dmpp)2] and [VO(maltolato)2], which have shown promising anti‐diabetic properties, to human serum albumin (HSA) in aqueous aerobic solution has been studied by 1H saturation transfer difference (STD) NMR spectroscopy and computational docking studies. Group epitope mapping and docking simulations indicate a preference of HSA binding to the 1:1 [VO2(dmpp)(OH)(H2O)]– and 1:2 [VO2(maltol)2]– vanadium(V) species. By using known HSA binders, competition NMR experiments revealed that both complexes preferentially bind to drug site I. Docking simulations carried out with HADDOCK together with restraints derived from the STD results led to three‐dimensional models that are in agreement with the NMR spectroscopic data, providing useful information on molecular interaction modes. These results indicate that the combination of STD NMR and data‐driven docking is a good tool for elucidating the interactions in protein–vanadium compounds and thus for clarifying the mechanism of drug delivery as vanadium compounds have shown potential therapeutic properties.
Synthesis of 6,6′‐Bis(dimethylamino)‐ and 6,6′‐Dibromo‐Substituted 2,2′‐Diphosphanylbiphenyls and Their Palladium Complexes
Authors: Petzold Holm , Alrawashdeh Albara I. S. , Heider Silvio , Haufe Linda , Rüffer Tobias
Published: July 2013

New 6,6′‐dibromo‐ and 6,6′‐bis(dimethylamino)‐substituted 2,2′‐diphosphanylbiphenyl ligands 11–14 were prepared starting from 2,2′‐dibromo‐4,4′‐dimethyl‐6,6′‐dinitro‐1,1′‐biphenyl (4). Depending on the phosphane groups [diphenylphosphanyl (11, 13) or diisopropylphosphanyl (12, 14)] the palladium dichloride complexes show different coordination symmetry. Whereas the smaller diphenylphosphanyl groups lead to C2‐symmetric complexes, the respective bis(diisopropyl)phosphanes 12 and 14 form C1‐symmetric complexes that show fluxional behavior due to the restricted rotation of the isopropyl groups as well as the exchange of atom positions within the C1‐symmetric conformer. All complexes have been tested as precatalysts in the Suzuki–Miyaura cross coupling reaction of 2‐bromotoluene and phenylboronic acid. The activity of the catalytic system increases with the size of the diphosphanes and the donating ability of the ligand. In contrast to C2‐symmetric palladium complex 15, platinum complex 19 was found to be C1‐symmetric in the solid state despite the fact that both complexes have the small bis(diphenylphosphanyl)‐substituted diphosphane ligand 11 in common. NiBr2 adduct 20 with a similar diphosphane 13 exists as a mixture of distorted square‐planar and tetrahedral coordination sphere geometries in equilibrium with each other.
Understanding the Ligand‐Directed Assembly of a Hexanuclear ThIV Molecular Cluster in Aqueous Solution
Authors: Hu Yung‐Jin , Knope Karah E. , Skanthakumar S. , Soderholm L.
Published: July 2013

The electrochemical hydrolysis of thorium(IV) was monitored by a combination of high‐energy X‐ray scattering (HEXS) and NMR spectroscopy. Once formed, μ2‐dihydroxo‐bridged dimers remain stable in solutions of moderate pH until glycine is added, upon which the dimers rapidly condense to form hexanuclear clusters [Th6(μ3‐O)4(μ3‐OH)4]12+. In the absence of the dimers or glycine, the clusters do not form even if the solutions are stored over extended times.
Generating omega‐3 rich olive oil by cross breeding
Authors: Ozdemir Yasin , Aktepe Tangu Nesrin , Akcay Mehmet E.
Published: July 2013

In this research, 14 hybrid table olive genotypes were used as material which were harvested from Olive Breeding Parcels in Atatürk Central Horticultural Research Institute (Yalova/TURKEY) and their maturation index, oil content, fatty acid composition and omega‐6:omega‐3 fatty acid ratio were evaluated. These genotypes were generated by crossing Gemlik, Manzanilla, Ascolana, Edinciksu, Uslu, and Tavşan yüreği olive cultivars during cross breeding studies of a national project. Oil was obtained from fruit of olive genotypes by cold pressing. Maturation index and oil content of genotypes were determined between 2.6–6.4 and 22.43–28.12 (%). Linolenic acid distributions in fatty acid composition of genotype's oil were detected between 0.5–1.33 (% in fatty acids). Some olive genotypes' oils had high linolenic characteristics that they have potential for supporting the necessary intake of omega‐3. Also, some of them have had the desired omega‐6/omega‐3 fatty acid ratio which were between 3.74 and 4.00.

Practical applications: Olive oil is a traditional product of Mediterranean basin and commonly consumed all over the world. But there is a need to improve yield, quality and nutritional value of olive oil. For this reason, there breeding studies were conducted. One of them was carried out in Ataturk Central Horticultural Research Institute. Here domestic and foreign olive cultivars were crossed to generate new olive genotypes since 1990. This research aimed to determine the olive oil of these obtained olive genotypes which had higher oil and omega‐3 content and lower omega‐6:omega‐3 fatty acid ratio. Generating the high omega‐3 content olive oil by cross breeding is one of the cheapest, simplest and most natural ways of obtaining omega‐3 and delivering it to the consumer.
Formulation and storage stability of baicalein‐loaded oil‐in‐water emulsions
Authors: Treesuwan Witcha , Ichikawa Sosaku , Wang Zheng , Neves Marcos A. , Uemura Kunihiko , Nakajima Mitsutoshi , Kobayashi Isao
Published: July 2013

Baicalein, a hydrophobic flavonoid, has been used in several traditional Chinese medicines. Baicalein is contained in the roots of Scutellariae radix and the fruits of Oroxylum indicum, called “phe kaa” in Thailand. Encapsulating baicalein in oil‐in‐water (O/W) emulsions could overcome its insolubility in water and is expected to provide new opportunities for food applications. This work seeks to formulate and characterize O/W emulsions loaded with baicalein. We investigated the effect of high‐pressure homogenization pressure on the droplet size, droplet size distribution, physical stability, and baicalein retention of these O/W emulsions. A refined soybean oil solution containing 0.05 wt% baicalein was used as the dispersed phase and an aqueous solution containing 1 wt% Tween 20 as the continuous phase. O/W emulsions with a surface‐weighted mean diameter (d3,2) of about 300 nm and a span of nearly two were formulated by high‐pressure homogenization at 60–150 MPa. The O/W emulsion droplets loaded with baicalein were physically stable in terms of variations in d3,2 and span during 30 days of storage in the dark at 4°C. HPLC analysis demonstrated that 77–84% of initial baicalein was retained in the fresh O/W emulsions, but that declined to 36–49% during storage.

Practical applications: O/W emulsions loaded with a functional flavonoid were produced by high‐pressure homogenization at different pressures. The findings obtained from this work may be of great interest for both scientific and industrial purposes, since formulation and stability were investigated. This food microstructuring technology could assist in the development of new food systems for nutrition therapy.
Synthesis of Thiol Esters Using Nano CuO/Ionic Liquid as an Eco‐Friendly Reductive System Under Microwave Irradiation
Authors: Azeredo Juliano B. , Godoi Marcelo , Schwab Ricardo S. , Botteselle Giancarlo V. , Braga Antonio L.
Published: July 2013

We report an efficient, fast, and environmentally friendly method for the synthesis of a wide range of thiol esters using stable diorganoyl disulfides and acyl chlorides, using CuO nanoparticles and [pmim]Br as the reductive system. This method gave good to excellent isolated yields of the desired products after only three minutes of microwave irradiation. Furthermore, by using the same green approach, we were also able to synthesize thiocarbonates bearing interesting functionalities.
Diaryldistyrylpyrazines: Solvatochromic and Acidochromic Fluorophores
Authors: Schmitt Volker , Moschel Sebastian , Detert Heiner
Published: July 2013

Diaryldimethylpyrazines are the starting materials for the synthesis ofC2‐symmetric donor‐ or acceptor‐substituted distyrylpyrazines. The optical properties of these cruciform‐shaped dyes are dominated by the distyrylpyrazine units; the photophysics is controlled by the styryl substitution, the diaryl substituents on the central pyrazine only having a small effect. Protonation occurs on the pyrazine and/or lateral amines or azines, thereby altering the absorption and emission properties. Hypso‐ and bathochromism as well as fluorescence quenching depend on the nature of the terminal substituent. This, and a significant positive solvatochromism of the fluorescence, allow optical sensing of the pH and polarity of the environment.
Regioselective Conjugate Addition of Nitriles to α,β‐Unsaturated Imines: Synthesis of Fluorinated Primary Enamines and 2‐Aminopyridine Derivatives
Authors: Fernández de Trocóniz Guillermo , Ochoa de Retana Ana M. , Pascual Sergio , Ezpeleta José M. , Palacios Francisco
Published: July 2013

The regioselective Michael addition of the carbanion of 2‐phenylacetonitrile (R2 = Ph) and malononitrile (R2 = CN) to fluoroalkylated α,β‐unsaturated imines 1 is described. Fluorinated imines 1 were used as intermediates for the regioselective 1,4‐addition and synthesis of functionalized fluorinated primary enamines 5 and 7, fluorine‐containing trans‐3,4‐dihydro‐2‐aminopyridines 2, and fluorinated 2‐aminopyridines 4 and 8, which were obtained with total atom economy. Derivatives 2 and 8 were also prepared by an intramolecular cyclocondensation reaction of functionalized fluorinated primary enamines 5 and 7, respectively, in the presence of a base (NaH).
Selectfluor‐Mediated Fluorination and C–C Bond Cleavage of Cyclohexene‐Fused Isoxazoline N‐Oxides
Authors: R.R. Rajawinslin , Raihan Mustafa J. , Janreddy Donala , Kavala Veerababurao , Kuo Chun‐Wei , Kuo Ting‐Shen , Chen Mei‐Ling , He Chiu‐Hui , Yao Ching‐Fa
Published: July 2013

A rapid method for the synthesis of long‐chain fluorinated compounds using a C–C bond‐cleavage reaction was developed. Selectfluor was the most effective fluorinating agent of those tested in this study. Long‐chain fluoro dioxo nitriles were formed from isoxazoline N‐oxides via nitroso intermediates.
Palladium‐Catalyzed Double Cross‐Coupling Reactions of Organodimetallic Reagents Leading to Polycyclic Aromatic Hydrocarbons
Authors: Shimizu Masaki , Hiyama Tamejiro
Published: July 2013

This microreview describes our contributions to the development of palladium‐catalyzed annulations of organodimetallic reagents with organic dihalides, which serve as versatile synthetic methods for functionalized polycyclic aromatic hydrocarbons. Presented first are palladium‐catalyzed double cross‐coupling reactions of 1,2‐diborylalkenes and ‐arenes with 2,2′‐dibromobiaryls and 1‐bromo‐2‐(2‐bromoethenyl)arenes, respectively. The next section describes palladium‐catalyzed coupling reactions between 9‐stannafluorenes and 1,2‐dibromoarenes, in which the 9‐stannafluorenes act as equivalents of 1,4‐dimetal reagents. The last section covers palladium‐catalyzed double cross‐coupling reactions variously between 1,2‐diboryl reagents and 1‐bromo‐2‐(bromomethyl)arenes, between 1,1‐diborylalk‐1‐enes and 2,2′‐dibromobiaryls, and between 9‐stannafluorenes and 1,1‐dibromoalk‐1‐enes, to form systems containing five‐membered rings in one‐step fashion.
Enzymatic Kinetic Resolution and Racemization of 2‐(Tetramethylpiperidine‐1‐oxyl)ethanols
Authors: Prechter Agnes , Heinrich Markus R.
Published: July 2013

The Candida antarctica lipase B catalyzed transesterification of 2‐(tetramethylpiperidine‐1‐oxyl)ethanols provides acetates in useful yields with good to high enantiomeric excess values. By taking advantage of the persistent radical effect, the remaining alcohols can be cleanly racemized under mild conditions in the presence of TEMPO [2,2,6,6‐tetramethylpiperidin‐1‐yl)oxidanyl].
Selective Synthesis of 5,6‐Dihydroindolo[1,2‐a]quinoxalines and 6,7‐Dihydroindolo[2,3‐c]quinolines by Orthogonal Copper and Palladium Catalysis
Authors: Zhang Lei , Zhao Fei , Zheng Mingyue , Zhai Yun , Wang Jiang , Liu Hong
Published: July 2013

In combination with the Ugi four‐component reaction, two important indole‐fused heterocycles have been prepared in two steps from readily accessible starting materials. From the same set of Ugi adducts 5, 5,6‐dihydroindolo[1,2‐a]quinoxalines 6 were rapidly generated in excellent yields by a copper‐catalyzed N–H arylation pathway, whereas 6,7‐dihydroindolo[2,3‐c]quinolones 7 were obtained by palladium‐catalyzed C–H arylations in good yields without the protection of the indole N1 moiety. Microwave heating was used to accelerate these intramolecular C–N and C–C bond‐forming reactions performed under controlled reaction conditions.
Oxazolidine Sulfur Ylides Derived from Phenylglycinol for the Specific and Highly Diastereoselective Synthesis of Aryl and Alkyl trans‐Epoxyamides
Authors: Gordillo Paola G. , Aparicio David M. , Flores Marcos , Mendoza Angel , Orea Laura , Juárez Jorge R. , Huelgas Gabriela , Gnecco Dino , Terán Joel L.
Published: July 2013

Aryl and alkyl chiral oxazolidine sulfonium salts with cis and trans dispositions derived from (–)‐(R)‐2‐phenylglycinol were demonstrated to be good to excellent chiral auxiliaries for the diastereoselective synthesis of (2R,3S)‐trans‐epoxyamides. Interestingly, the diastereoselective outcome depends on the stereochemistry of the chiral center at the C‐4 position of the oxazole moiety. The stereoselectivities were consistent even for aliphatic aldehydes.
Transport of Cesium Ion Across a Bilayer Lipid Membrane and Its Facilitation in the Presence of Iodide Ion
Authors: Shirai Osamu , Ohnuki Toshihiko , Kitazumi Yuki , Kano Kenji
Published: July 2013

The ion transport current was clearly observed across a bilayer lipid membrane (BLM) between two aqueous phases (W1, W2) containing 0.1 M CsCl. This indicates that Cs+ can spontaneously penetrate the BLM in the absence of any kind of transporter. In addition, the current density at a given potential between W1 and W2 increased using I− instead of Cl− as the counter ion. Our results strongly suggest that the cell membrane transport is partially responsible for the internal exposure of 134Cs and 137Cs.
A Highly Sensitive Method for Determination of Monobutyltin in Aqueous Media by Stripping Voltammetry at a Renewable Silver Amalgam Annular Band Electrode
Authors: Niewiara Ewa
Published: July 2013

An adsorptive stripping voltammetric (AdSV) procedure for the determination of monobutyltin in aqueous media at a silver liquid amalgam film‐modified silver solid amalgam annular band electrode (AgLAFAgSAE) is described. Determination of monobutyltin proceeds in two steps. At the beginning monobutyltin ions (BuSn3+) are accumulated from 0.1 M NH4NO3 and 10 % ethanol solution at a potential of −0.2 V, than the BuSn0 film is preconcentrated at the working electrode surface at a potential of −0.7 V. After this step the DP AdSV voltammogram is recorded. The analytical parameters and the procedure of the electrode regeneration and activation were optimized. The calibration curve of monobutyltin in the range 0.02–0.30 mg L−1 is linear (r=0.9973). The detection limit for 5 s of preconcentration, calculated as 3σ of the blank was equal to 0.004 mg L−1, repeatability of the peak current was 1.8 % (n=5). Repeatability and sensitivity of monobutyltin determination depends strongly on the analyzed solution properties, measurement conditions and the working electrode quality. The proposed procedure was tested by means of monobutyltin determination in tap waters.
The use of polyurethane as an elastomer in thermoplastic microfluidic devices and the study of its creep properties
Authors: Gu Pan , Nishida Toshikazu , Fan Z. Hugh
Published: July 2013

We report using polyurethane (PU) as an elastomer in microvalves integrated with thermoplastic microfluidic devices. Elastomer‐based microvalves have been used in a number of applications and the elastomer often used is PDMS. Although it is a convenient material for prototyping, PDMS has been recognized to possess shortcomings such as solvent incompatibility and unfavorable manufacturability. We investigated the use of PU as an elastomer to address the challenges. A reliable method was developed to bond hybrid materials such as PU and cyclic olefin copolymer. The film thickness from 3.5 to 24.5 μm was studied to identify an appropriate thickness of PU films for desirable elasticity in microvalves. We integrated PU with thermally actuated, elastomer‐based microvalves in thermoplastic devices. Valve actuations were demonstrated, and the relationship between the valve actuation time and heater power was studied. We compared PU with PDMS in terms of their microvalve performance. Valves with PDMS failed to function after two weeks since the thermal‐sensitive solution evaporated through porous PDMS membrane, whereas the same valve with PU functioned properly after eight months. In addition, we evaluated the creep and creep recovery of PU, which is a common phenomenon of viscoelastic materials and is related to the long‐term elastic property of PU after prolonged use.
Application of an improved magnetic immunosorbent in an Ephesia chip designed for circulating tumor cell capture
Authors: Svobodova Zuzana , Kucerova Jana , Autebert Julien , Horak Daniel , Bruckova Lenka , Viovy Jean‐Louis , Bilkova Zuzana
Published: July 2013

In this study, we describe a particular step in developing a microfluidic device for capture and detection of circulating tumor cells—specifically the preparation of an immunosorbent for implementation into the separation chip. We highlight some of the most important specifics connected with superparamegnetic microspheres for microfluidic purposes. Factors such as nonspecific adsorption on microfluidic channels, interactions with model cell lines, and tendency to aggregation were investigated. Poly(glycidyl methacrylate) microspheres with carboxyl groups were employed for this purpose. To address the aforementioned challenges, the microspheres were coated with hydrazide‐PEG‐hydrazide, and subsequently anti‐epithelial cell adhesion molecule (EpCAM) antibody was immobilized. The prepared anti‐EpCAM immunosorbent was pretested using model cell lines with differing EpCAM density (MCF7, SKBR3, A549, and Raji) in a batchwise arrangement. Finally, the entire system was implemented and studied in an Ephesia chip and an evaluation was performed by the MCF7 cell line.
Liposomal nanotransporter for targeted binding based on nucleic acid anchor system
Authors: Nejdl Lukas , Merlos Rodrigo Miguel Angel , Kudr Jiri , Ruttkay‐Nedecky Branislav , Konecna Marie , Kopel Pavel , Zitka Ondrej , Hubalek Jaromir , Kizek Rene , Adam Vojtech
Published: July 2013

Microfluidic techniques have been developed intensively in recent years due to lower reagent consumption, faster analysis, and possibility of the integration of several analytical detectors into one chip. Electrochemical detectors are preferred in microfluidic systems, whereas liposomes can be used for amplification of the electrochemical signals. The aim of this study was to design a nanodevice for targeted anchoring of liposome as transport device. In this study, liposome with encapsulated Zn(II) was prepared. Further, gold nanoparticles were anchored onto the liposome surface allowing binding of thiol moiety‐modified molecules (DNA). For targeted capturing of the transport device, DNA loops were used. DNA loops were represented by paramagnetic microparticles with oligo(DT)25 chain, on which a connecting DNA was bound. Capturing of transport device was subsequently done by hybridization to the loop. The individual steps were analyzed by electrochemistry and UV/Vis spectrometry. For detection of Zn(II) encapsulated in liposome, a microfluidic system was used. The study succeeded in demonstrating that liposome is suitable for the transport of Zn(II) and nucleic acids. Such transporter may be used for targeted binding using DNA anchor system.