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Polar
Terms modified by Polar Selected AbstractsMolecular polarizability of fullerenes and endohedral metallofullerenesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 11 2002Francisco Torrens Abstract The interacting induced dipoles polarization model implemented in our program POLAR is used for the calculation of the molecular dipole µ and tensor quadrupole moments and also the dipole,dipole polarizability . The method is tested with Scn, Cn (fullerene and graphite) and endohedral Scn@Cm clusters. The polarizability is an important quantity for the identification of clusters with different numbers of atoms and even for the separation of isomers. The results for the polarizability are of the same order of magnitude as from reference calculations performed with our version of the program PAPID. The bulk limit for the polarizability is estimated from the Clausius,Mossotti relationship. The polarizability trend for these clusters as a function of size is different from what one might have expected. The clusters are more polarizable than what one might have inferred from the bulk polarizability. Previous theoretical work yielded the same trend for Sin, Gen and GanAsm small clusters. However, previous experimental work yielded the opposite trend for Sin, GanAsm and GenTem larger clusters. At present, the origin of this difference is problematic. One might argue that smaller clusters need not behave like those of intermediate size. The high polarizability of small clusters is attributed to dangling bonds at the surface of the cluster. In this respect, semiconductor clusters resemble metallic clusters. Copyright © 2002 John Wiley & Sons, Ltd. [source] Measuring and modelling the performance of a parallel ODMG compliant object database serverCONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 1 2006Sandra de F. Mendes Sampaio Abstract Object database management systems (ODBMSs) are now established as the database management technology of choice for a range of challenging data intensive applications. Furthermore, the applications associated with object databases typically have stringent performance requirements, and some are associated with very large data sets. An important feature for the performance of object databases is the speed at which relationships can be explored. In queries, this depends on the effectiveness of different join algorithms into which queries that follow relationships can be compiled. This paper presents a performance evaluation of the Polar parallel object database system, focusing in particular on the performance of parallel join algorithms. Polar is a parallel, shared-nothing implementation of the Object Database Management Group (ODMG) standard for object databases. The paper presents an empirical evaluation of queries expressed in the ODMG Query Language (OQL), as well as a cost model for the parallel algebra that is used to evaluate OQL queries. The cost model is validated against the empirical results for a collection of queries using four different join algorithms, one that is value based and three that are pointer based. Copyright © 2005 John Wiley & Sons, Ltd. [source] Square-Planar Noble Metal Iodate [M(IO3)4]n, (M = PdII, AuIII; n = 2, 1) Anions and Their Ability to Form Polar and Centrosymmetric ArchitecturesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2007Jie Ling Abstract K+ salts of the square-planar noble metal iodate [M(IO3)4]n, (M = PdII, AuIII; n = 2, 1) anions have been prepared under mild hydrothermal conditions, and the structures elucidated to demonstrate that while both are highly polar anions, polar and centrosymmetric extended architectures can form using these building units. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] NMR Enantiodiscrimination of Polar and Apolar Substrates by Multifunctional CyclodextrinsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2005Gloria Uccello-Barretta Abstract Mixed methylated/carbamoylated cyclodextrins constitute a new class of chiral complexing agents for NMR spectroscopy, which are able to induce anisochrony of enantiomeric mixtures of apolar trisubstituted allenes and polar derivatized compounds most of which are endowed with a ,-acidic 3,5-dinitrophenyl ring. The differing contribution to enantiorecognition phenomena of the nature and location of the functional groups on the two cyclodextrin rims was shown. Some interesting aspects of the complexation phenomena, which are the basis of chiral recognition, have been underlined by NMR spectroscopic investigations.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] North American weather-type frequency and teleconnection indicesINTERNATIONAL JOURNAL OF CLIMATOLOGY, Issue 1 2003Scott C. Sheridan Abstract The impact of teleconnections upon the surface climate has largely been examined via a response in monthly mean temperature or total precipitation. In this paper, a different approach is undertaken, by examining the response of synoptic weather-type frequencies to different teleconnection phases. For over 330 stations in the USA and Canada, the Spatial Synoptic Classification scheme has classified each day in each station's period of record into one of seven weather-type categories, based on thermal, moisture, and other characteristics. The differences in how frequently these different weather types occur in different phases of the North Atlantic Oscillation (NAO) and Pacific,North American (PNA) teleconnection patterns is assessed, for Canadian stations from 1953 to 1993, and for US stations from 1950 to 1999. For PNA, a significant shift in the transitional frequency is observed, suggesting changes in storm track. Concomitantly, a large shift in Dry Polar and Moist Tropical frequencies is observed across the continent. Across the West, in +PNA wintertime months far fewer Dry Polar days are observed. Across the eastern USA, these polar intrusions are more common, and Moist Tropical is diminished significantly. The frequency of the transitional situation is also correlated with NAO phase, with differences as large as a factor of two across much of Canada and the northern USA. In northeastern Canada, there is a large replacement of Moist Polar conditions with Dry Polar conditions during +NAO. Farther south, however, across the eastern USA, both polar weather types occur much less often with +NAO. Although previous research has discovered eastern North American connections to the NAO, this research has shown that the connections often extend into the interior West during much of the year. Particularly strong in the spring, Dry Tropical conditions are much more common with +NAO throughout much of the continent, as far west as the Great Basin. Copyright © 2003 Royal Meteorological Society. [source] rRNA PROBES FOR IDENTIFICATION AND CHARACTERIZATION OF MARINE PHYTOPLANKTON: THEIR POTENTIAL APPLICATION FOR DNA MICROCHIPSJOURNAL OF PHYCOLOGY, Issue 2001Article first published online: 24 SEP 200 Groben R., Lange, M. & Medlin, L. K. Alfred Wegener Institute for Polar and Marine Research, Am Handelshafen 12, D-27570 Bremerhaven, Germany A fast and reliable identification of nano- and picoplankton by light microscopy is often difficult because of the lack of usable morphological characteristics, whereas electron microscopy and biochemical methods are very time consuming. Identification of toxic algae also requires a great deal of taxonomic experrtise so that false positives are not recorded. One solution is to use taxon specific rRNA probes. For this purpose we designed probes for phytoplankton taxa, including toxic algae. These probes were either labelled with Digoxigenin (DIG) and used in DNA dot blot experiments, or labelled with fluorochromes and used in whole-cell hybridisations with fluorescence microscopy or flow cytometric detection. Specific probes could be used over a broad taxonomic range from higher groups (i.e. the class of dinoflagellates) to species level (i.e. Prorocentrum lima). These probes were be used in the EU MAST project AIMS for the development of an automated identification system for marine phytoplankton in combination with flow cytometry and artificial neural networks (ANNs), in the EU MAST DETAL and in the German national project (TEPS) for the development of an early warning system for harmful algal blooms. Results using Digoxigenin (DIG)-labelled probes on picoplankton samples taken from several water bodies indicate that hierarchial re-probing of spotted samples can be achieved and this suggests that probes can be adapted to DNA microchips. Preliminary field results for a hand-held DNA microchip reader are presented. This work was supported by the German BMBF TEPS 03F0161 and the EU AIMS MAS3-CT97-0080 and EU DETAL Q5RS-2000-30778 projects. [source] Determination of nonsteroidal antiinflammatory drugs in water samples using liquid chromatography coupled with diode-array detector and mass spectrometryJOURNAL OF SEPARATION SCIENCE, JSS, Issue 17 2005Jolanta Debska Abstract An analytical method for the determination of trace levels of six different nonsteroidal antiinflammatory drugs (NSAIDs) in water samples has been developed and validated. Environmentally relevant pharmaceuticals were chosen according to human consumption in Poland. Final analysis of the target compounds was performed by RP LC,diode-array detection,MS, whereas sample preparation included an SPE step. For this SPE step, a number of packing materials, such as LiChrolut RP-18, calixarene, Strata-X, BAKERBOND Narc-2, BAKERBOND Polar Plus, BAKERBOND styrene divinylbenzene-1, and Discovery DSC-18, were used, and their respective advantages and disadvantages in this study were discussed. The RP-18 phase was found to be the most retentive for all analytes. The detection limits for compounds in surface waters were varied from 0.005 for diflunisal to 0.095 ,g/L for ibuprofen. The average recoveries of NSAIDs from the surface water samples ranged from 80 up to 103%. RSD value is relatively low (from 4% for fenoprofen up to 8% for ibuprofen). The performance of the method was tested with several environmental water samples. [source] Synthesis of Polar and Non-Polar Nano-Corundum and Uses for Aluminium Carboxylate Hybrid Nanocomposites with Enhanced Surface Mechanical and Viscoelastic PropertiesMACROMOLECULAR MATERIALS & ENGINEERING, Issue 10-11 2007Hans-Jürgen Gläsel Abstract Amorphous aluminium carboxylate nanoparticles were checked for their potential as precursors for nano-corundum powders prepared by a high-temperature conversion process. Exemplifying x-ray photoelectron spectroscopy studies of the aluminium carboxylate nanoparticles with polar and non-polar ligands showed that, during the course of the high-temperature treatment, specific features of the ultrafine organo-aluminium powders such as polarity/non-polarity and concomitant hydrophilic/hydrophobic properties were preserved. The resulting nano-corundum powders were in turn identified as positive synergists for the enforcement of radiation-cured aluminium carboxylate/acrylate coatings. The simultaneous (optional) use of micro-corundum particles yielded polymer hybrid coatings. In comparison to acrylate-based organo-aluminium nanocomposites, polymeric hybrid coatings revealed significantly improved surface mechanical and viscoelastic properties. In addition to acrylate coatings, other polar and even non-polar bulk polymers were subject to nano/micro modification using polar and non-polar nano-corundum powders, respectively. [source] How do helix,helix interactions help determine the folds of membrane proteins?PROTEIN SCIENCE, Issue 4 2003Perspectives from the study of homo-oligomeric helical bundles FRET, fluorescence resonance energy transfer; NBD, 7-nitrobenz-2-oxa-1,3-diazole; C-14 betaine, N -tetradecyl- N,N -dimethyl-3-ammonio-1-propanesulfonate; MF, mole fraction Abstract The final, structure-determining step in the folding of membrane proteins involves the coalescence of preformed transmembrane helices to form the native tertiary structure. Here, we review recent studies on small peptide and protein systems that are providing quantitative data on the interactions that drive this process. Gel electrophoresis, analytical ultracentrifugation, and fluorescence resonance energy transfer (FRET) are useful methods for examining the assembly of homo-oligomeric transmembrane helical proteins. These methods have been used to study the assembly of the M2 proton channel from influenza A virus, glycophorin, phospholamban, and several designed membrane proteins,all of which have a single transmembrane helix that is sufficient for association into a transmembrane helical bundle. These systems are being studied to determine the relative thermodynamic contributions of van der Waals interactions, conformational entropy, and polar interactions in the stabilization of membrane proteins. Although the database of thermodynamic information is not yet large, a few generalities are beginning to emerge concerning the energetic differences between membrane and water-soluble proteins: the packing of apolar side chains in the interior of helical membrane proteins plays a smaller, but nevertheless significant, role in stabilizing their structure. Polar, hydrogen-bonded interactions occur less frequently, but, nevertheless, they often provide a strong driving force for folding helix,helix pairs in membrane proteins. These studies are laying the groundwork for the design of sequence motifs that dictate the association of membrane helices. [source] Lipid characterization of both wild and cultured eggs of cuttlefish (Sepia officinalis L.) throughout the embryonic developmentAQUACULTURE NUTRITION, Issue 1 2009A.V. SYKES Abstract The present work reports a characterization of mean wet weight and moisture, the lipid class and fatty acid (FA) composition from the total lipids (TL), of both culture and wild eggs of the cuttlefish, Sepia officinalis, throughout the embryonic development. Additionally, reproductive data, such as the number of spawnings, number and mean weight of eggs and duration of spawning period of cultured cuttlefish is provided. Both types of eggs were similar in mean wet weight, moisture content, TL content and lipid composition throughout embryonic development. Females from the cultured group spawned 13 times and laid 8654 eggs in 64 days, with a mean weight of 0.607 ± 0.179 g. A sex ratio of 1.57 (11, for 7,) promoted an individual fecundity of 787 eggs/, (the biggest until now on our culture facilities), which might be related to increased bottom areas. The TL increased with day/stage of embryonic development (P < 0.05) only in the cultured egg group. However, no differences were found on TL between culture and wild eggs at the same day/stage (P > 0.05). Eggs displayed predominant levels of phosphatidylcholine, phosphatidylethanolamine (PE), cholesterol and triacylglycerol at the end of embryonic development. Polar and neutral lipids of both eggs groups remained consistently proportional (,50% for each lipid fraction) and a significant increase (P < 0.05) was observed in phosphatidylserine, PE and free FA throughout the embryonic development. In either egg type and day, 16:0, 18:0, 20:5n-3 and 22:6n-3 accounted for approximately 70 g Kg,1 of all FA and saturated and n-3 totals seemed to have the same proportion in the cuttlefish eggs. The present results suggest that lipids are not used as energetic substrate but as structural components in cuttlefish egg. [source] From Reflection to Refraction: Rethinking Paradigms of Cultural Interaction and Identity in Peru and MexicoBULLETIN OF LATIN AMERICAN RESEARCH, Issue 4 2002Melisa Moore This article explores the construction and reworking of paradigms of culture contact and identity by social scientists and cultural critics in response to contradictory sociocultural experiences of modernity in Peru and Mexico. It seeks to do so in the context of calls made by the Peruvian critic Antonio Cornejo Polar for greater historicism and critical thinking about these, and the concern that this appeal has since generated in the field of Latin American Cultural Studies. Focusing first on the postcolonial, ideologically driven model of ,mestizaje', the article then traces continuities and discontinuities between it and latter,day thinking about cultural pluralism. [source] ChemInform Abstract: A Polar and Chiral Indium Telluride Featuring Supertetrahedral T2 Clusters and Nonlinear Optical Second Harmonic Generation.CHEMINFORM, Issue 13 2009Qichun Zhang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Insertion of Polar and Nonpolar Unsaturated Molecules into Carbon,Rhenium Bonds Generated by C,H Bond Activation: Synthesis of Phthalimidine and Indene Derivatives.CHEMINFORM, Issue 21 2006Yoichiro Kuninobu Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Addressing Association Entropy by Reconstructing Guanidinium Anchor Groups for Anion Binding: Design, Synthesis, and Host,Guest Binding Studies in Polar and Protic SolutionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 20 2008Vinod Abstract The bicyclic hexahydropyrimidino[1,2a]pyrimidine cationic scaffold has a well-known capacity to bind a variety of oxoanions (phosphates, carboxylates, squarates, phosphinates). Based on this feature, the parent host was supplemented with sec -carboxamido substituents to generate compounds 1,3 in an effort to improve the anion-binding affinity and selectivity and to learn about the role and magnitude of entropic factors. Bicyclic guanidinium compounds were prepared by a convergent strategy via the corresponding tetraester 22 followed by catalytic amidation. Host,guest binding studies with isothermal titration calorimetry in acetonitrile probed the behavior of artificial hosts 1,3 in comparison with the tetraallylguanidinium compound 4 on binding p -nitrobenzoate, dihydrogenphosphate, and 2,2,-bisphenolcyclophosphate guests that showed enhanced affinities in the 105,106,M,1 range. Contrary to expectation, better binding emerges from more positive association entropies rather than from stronger enthalpic interactions (hydrogen bonding). In an NMR spectroscopy titration in DMSO, o -phthalate was sufficiently basic to abstract a proton from the guanidinium function, as confirmed by an X-ray crystal structure of the product. The novel carboxamide-appended anchor groups also bind carboxylates and phosphates, but not hydrogen sulfate in methanol with affinities in excess of 104,M,1. The energetic signature of the complexation in methanol is inverted with respect to acetonitrile solvent and shows a pattern of general ion pairing with strong positive entropies overcompensating endothermic binding enthalpies. This study provides an example of the fact that bona fide decoration of a parent guanidinium anchor function with an additional binding functionality may provide the desired enhancement of the host,guest affinity, yet for a different reason than that implemented by design as guided by standard molecular modeling. [source] Force Field Evaluation for Biomolecular Simulation: Free Enthalpies of Solvation of Polar and Apolar Compounds in Various SolventsCHEMPHYSCHEM, Issue 3 2006Daan P. Geerke Abstract Recently, the GROMOS biomolecular force field parameter set 53A6,which has been parametrized to reproduce experimentally determined free enthalpies of hydration and solvation in cyclohexane of amino acid side-chain analogs,was presented. To investigate the transferability of the new parameter set, we calculated free enthalpies of solvation of a range of polar and apolar compounds in different solvents (methanol, dimethyl sulfoxide (DMSO), acetonitrile, and acetone) from molecular dynamics simulations using the GROMOS 53A6 force field. For methanol and DMSO, parameters were used that are available in the 53A6 parameter set. For acetonitrile, a recently developed model was taken and for acetone, two models available in literature were used. We found that trends in and values for the solvation free enthalpies are in satisfactory agreement with experiment, except for the solvation in acetone for which deviations from experiment can be explained in terms of the properties of the models used. [source] Predicting summer rainfall in the Yangtze River basin with neural networksINTERNATIONAL JOURNAL OF CLIMATOLOGY, Issue 7 2008Heike Hartmann Abstract Summer rainfall in the Yangtze River basin is predicted using neural network techniques. Input variables (predictors) for the neural network are the Southern Oscillation Index (SOI), the East Atlantic/Western Russia (EA/WR) pattern, the Scandinavia (SCA) pattern, the Polar/Eurasia (POL) pattern and several indices calculated from sea surface temperatures (SST), sea level pressures (SLP) and snow data from December to April for the period from 1993 to 2002. The output variable of the neural network is rainfall from May to September for the period from 1994 to 2002, which was previously classified into six different regions by means of a principal component analysis (PCA). Rainfall is predicted from May to September 2002. The winter SST and SLP indices are identified to be the most important predictors of summer rainfall in the Yangtze River basin. The Tibetan Plateau snow depth, the SOI and the other teleconnection indices seem to be of minor importance for an accurate prediction. This may be the result of the length of the available time series, which does not allow a deeper analysis of the impact of multi-annual oscillations. The neural network algorithms proved to be capable of explaining most of the rainfall variability in the Yangtze River basin. For five out of six regions, our predictions explain at least 77% of the total variance of the measured rainfall. Copyright © 2007 Royal Meteorological Society [source] The embedded ion method: A new approach to the electrostatic description of crystal lattice effects in chemical shielding calculationsCONCEPTS IN MAGNETIC RESONANCE, Issue 5 2006Dirk Stueber Abstract The nuclear magnetic shielding anisotropy of NMR active nuclei is highly sensitive to the nuclear electronic environment. Hence, measurements of the nuclear magnetic shielding anisotropy represent a powerful tool in the elucidation of molecular structure for a wide variety of materials. Quantum mechanical ab initio nuclear magnetic shielding calculations effectively complement the experimental NMR data by revealing additional structural information. The accuracy and capacity of these calculations has been improved considerably in recent years. However, the inherent problem of the limitation in the size of the systems that may be studied due to the relatively demanding computational requirements largely remains. Accordingly, ab initio shielding calculations have been performed predominantly on isolated molecules, neglecting the molecular environment. This approach is sufficient for neutral nonpolar systems, but leads to serious errors in the shielding calculations on polar and ionic systems. Conducting ab initio shielding calculations on clusters of molecules (i.e., including the nearest neighbor interactions) has improved the accuracy of the calculations in many cases. Other methods of simulating crystal lattice effects in shielding calculations that have been developed include the electrostatic representation of the crystal lattice using point charge arrays, full ab initio methods, ab initio methods under periodic boundary conditions, and hybrid ab initio/molecular dynamics methods. The embedded ion method (EIM) discussed here follows the electrostatic approach. The method mimics the intermolecular and interionic interactions experienced by a subject molecule or cluster in a given crystal in quantum mechanical shielding calculations with a large finite, periodic, and self-consistent array of point charges. The point charge arrays in the EIM are generated using the Ewald summation method and embed the molecule or ion of interest for which the ab initio shielding calculations are performed. The accuracy with which the EIM reproduces experimental nuclear magnetic shift tensor principal values, the sensitivity of the EIM to the parameters defining the point charge arrays, as well as the strengths and limitations of the EIM in comparison with other methods that include crystal lattice effects in chemical shielding calculations, are presented. © 2006 Wiley Periodicals, Inc. Concepts Magn Reson Part A 28A: 347,368, 2006 [source] Interdiffusion phenomena in InGaAs/GaAs superlattice structuresCRYSTAL RESEARCH AND TECHNOLOGY, Issue 5 2010B. Sar, kavak Abstract We have studied structural properties of InGaAs/GaAs superlattice sample prepared by Molecular Beam Epitaxy (MBE) using high resolution X-ray diffractometer (HRXRD). Increasing strain relaxation and defect generations are observed with the increasing Rapid Thermal Annealing (RTA) temperature up to 775 °C. The higher temperatures bring out relaxation mechanisms; interdiffusion and favored migration. The defect structure and the defects which are observed with the increasing annealing temperature were analyzed. Firstly, the in-plane and out-of-plane strains after the annealing of sample were found. Secondly, the structural defect properties such as the parallel X-ray strain, perpendicular X-ray strain, misfit, degree of relaxation, x composition, tilt angles and dislocation that are obtained from X-ray diffraction (XRD) analysis were carried out at every temperature. As a result, we observed that the asymmetric peaks especially in asymmetric (224) plane was affected more than symmetric and asymmetric planes with lower polar or inclination angles due to c-direction at low temperature. These structural properties exhibit different unfavorable behaviors for every reflection direction at the increasing temperatures. The reason is the relaxation which is caused by spatially inhomogeneous strain distribution with the increasing annealing temperature. In the InGaAs superlattice samples, this process enhances preferential migration of In atoms along the growth direction. Further increase in the annealing temperature leads to the deterioration of the abrupt interfaces in the superlattice and degradation in its structural properties. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Crystal growth, crystal structure and physical properties of polar orthorhombic tris(glycine) zinc chlorideCRYSTAL RESEARCH AND TECHNOLOGY, Issue 2 2008M. Fleck Abstract Large single crystals of the polar (point group mm 2) compound tris(glycine) zinc chloride, (NH3CH2COO)3 · ZnCl2, were grown from aqueous solutions. The refractive indices were measured in the wavelength region from 365 nm to 1083 nm and an unpolarised absorption spectrum was recorded (transparency range from 260 to 1550nm). The phase matching conditions for second harmonic generation were analysed: both, type I (ss-f) and type II (sf-f) are possible in the red and near IR region. All five components of the piezoelectric tensor [dijk ] were determined; the maximum values of longitudinal and transverse piezoelectric effects are less than one half of d111 of ,-quartz. In addition, a redetermination of the crystal structure (including location of H atoms) is presented. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Alkanethiols Modified Gold Electrodes for Selective Detection of Molecules with Different Polarity and Molecular Size.ELECTROANALYSIS, Issue 3-5 2009Application to Vitamin B2 Analysis Abstract The cyclic voltammetry behavior of several molecules with different polarity and molecular size on gold electrodes modified with nonfunctionalized alkanethiols of different chain length, usually employed as chromatographic stationary phases, are studied. The redox systems hexacyanoferrate(II/III), ferrocene/ferrocine and hydroquinone/quinone are chosen as template molecules. As modifiers, ethanethiol, 1-octanethiol and di- n -octadecyldisulfide are selected. We can conclude that polar molecules can reach the electrode surface through channels created by the modifiers. However, when nonpolar compounds are analyzed, the nonpolar interactions between the analyte and the terminal group of the modifier lead to retention of the compound, retarding its arrival to the electrode surface. A molecule with polar and nonpolar part was used for the application of this conclusion. If the gold electrode is modified with di- n -octadecyldisulfide, the electrochemical behavior of vitamin B2 becomes simpler than that observed on a bare one. This result allows a sensitive and selective procedure to be developed for direct determination of vitamin B2 in pharmaceutical formulations. [source] CE coupled to MALDI with novel covalently coated capillariesELECTROPHORESIS, Issue 4 2010Stefan Bachmann Abstract CE offers the advantage of flexibility and method development options. It excels in the area of separation of ions, chiral, polar and biological compounds (especially proteins and peptides). Masking the active sites on the inner surface of a bare fused silica capillary wall is often necessary for CE separations of basic compounds, proteins and peptides. The use of capillary surface coating is one of the approaches to prevent the adsorption phenomena and improve the repeatability of migration times and peak areas of these analytes. In this study, new capillary coatings consisting of (i) derivatized polystyrene nanoparticles and (ii) derivatized fullerenes were investigated for the analysis of peptides and protein digest by CE. The coated capillaries showed excellent run-to-run and batch-to-batch reproducibility (RSD of migration time ,0.5% for run-to-run and ,9.5% for batch-to-batch experiments). Furthermore, the capillaries offer high stability from pH 2.0 to 10.0. The actual potential of the coated capillaries was tested by combining CE with MALDI-MS for analysing complex samples, such as peptides, whereas the overall performance of the CE-MALDI-MS system was investigated by analysing a five-protein digest mixture. Subsequently, the peak list (peptide mass fingerprint) generated from the mass spectra of each fraction was entered into the Swiss-Prot database in order to search for matching tryptic fragments using the MASCOT software. The sequence coverage of analysed proteins was between 36 and 68%. The established technology benefits from the synergism of high separation efficiency and the structure selective identification via MS. [source] Two variable semi-empirical and artificial neural-network-based modeling of peptide mobilities in CZE: The effect of temperature and organic modifier concentrationELECTROPHORESIS, Issue 5 2009Stefan Mittermayr Abstract This work was focused on investigating the effects of two separation influencing parameters in CZE, namely temperature and organic additive concentration upon the electrophoretic migration properties of model tripeptides. Two variable semi-empirical (TVSE) models and back-propagation artificial neural networks (ANN) were applied to predict the electrophoretic mobilities of the tripeptides with non-polar, polar, positively charged, negatively charged and aromatic R group characteristics. Previously published work on the subject did not account for the effect of temperature and buffer organic modifier concentration on peptide mobility, in spite of the fact that both were considered to be influential factors in peptide analysis. In this work, a substantial data set was generated consisting of actual electrophoretic mobilities of the model tripeptides in 30,mM phosphate buffer at pH 7.5, at 20, 25, 30, 35 and 40°C and at four different organic additive containing running buffers (0, 5, 10 and 15% MeOH) applying two electric field strengths (12 and 16,kV) to assess our mobility predicting models. Based on the Arrhenius plots of natural logarithm of mobility versus reciprocal absolute temperature of the various experimental setups, the corresponding activation energy values were derived and evaluated. Calculated mobilities by TVSE and back-propagation ANN models were compared with each other and to the experimental data, respectively. Neural network approaches were able to model the complex impact of both temperature and organic additive concentrations and resulted in considerably higher predictive power over the TVSE models, justifying that the effect of these two factors should not be neglected. [source] Cover Picture: Electrophoresis 18'2008ELECTROPHORESIS, Issue 18 2008Article first published online: 10 OCT 200 Issue number 18 is a Special Issue on "CE and CEC Innovations" consisting of 26 papers arranged into six sections. This Issue has one review article on the application of modern separation techniques in metabonomics, while the remaining articles pertain to microfluidics and miniaturization, novel trends in fundamentals and methodologies, various aspects of capillary coatings, open tubular CEC, MIP-CE, polar and nonpolar monoliths, MEEKC, MEKC and enantioseparations by CE and CEC. In addition Issue 18 has a "Fast Track" article on the CE-based assay of sirtuin enzymes. [source] Polar stationary phases for capillary electrochromatographyELECTROPHORESIS, Issue 23-24 2004Chuanhui Xie Abstract This review article summarizes the variety of polar stationary phases that have been employed for capillary electrochromatographic separations. Compared with reversed-phase stationary phases, the polar alternatives provide a completely different retention selectivity towards polar and charged analytes. Different types of polar stationary phases are reviewed, including the possible retention mechanisms. Electrochromatographic separations of polar solutes, peptides, and basic pharmaceuticals on polar stationary phases are presented. [source] Maintenance of narrow diet breadth in the monarch butterfly caterpillar: response to various plant species and chemicalsENTOMOLOGIA EXPERIMENTALIS ET APPLICATA, Issue 2-3 2002Danel B. Vickerman Abstract In order to better understand the maintenance of a fairly narrow diet breadth in monarch butterfly larvae, Danaus plexippus L. (Lepidoptera: Nymphalidae: Danainae), we measured feeding preference and survival on host and non-host plant species, and sensitivity to host and non-host plant chemicals. For the plant species tested, a hierarchy of feeding preferences was observed; only plants from the Asclepiadaceae were more or equally preferred to Asclepias curassavica, the common control. The feeding preferences among plant species within the Asclepiadaceae are similar to published mean cardenolide concentrations. However, since cardenolide data were not collected from individual plants tested, definitive conclusions regarding cardenolide concentrations and plant acceptability cannot be made. Although several non-Asclepiadaceae were eaten in small quantities, all were less preferred to A. curassavica. Additionally, these non-Asclepiadaceae do not support continued feeding, development, and survival of first and fifth-instar larvae. Preference for a host versus a non-host (A. curassavica versus Vinca rosea) increased for A. curassavica reared larvae as compared to diet-reared larvae suggesting plasticity in larval food preferences. Furthermore, host species were significantly preferred over non-host plant species in bioassays using a host plant or sucrose as a common control. Larval responses to pure chemicals were examined in order to determine if host and non-host chemicals stimulate or deter feeding in monarch larvae. We found that larvae were stimulated to feed by some ubiquitous plant chemicals, such as sucrose, inositol, and rutin. In contrast, several non-host plant chemicals deterred feeding: caffeine, apocynin, gossypol, tomatine, atropine, quercitrin, and sinigrin. Additionally the cardenolides digitoxin and ouabain, which are not in milkweed plants, were neutral in their influence on feeding. Another non-milkweed cardenolide, cymarin, significantly deterred feeding. Extracts of A. curassavica leaves were tested in bioassays to determine which components of the leaf stimulate feeding. Both an ethanol extract of whole leaves and a hexane leaf-surface extract are phagostimulatory, suggesting the involvement of both polar and non-polar plant compounds. These data suggest that the host range of D. plexippus larvae is maintained by both feeding stimulatory and deterrent chemicals in host and non-host plants. [source] Ecological niche partitioning in the picoplanktonic green alga Micromonas pusilla: evidence from environmental surveys using phylogenetic probesENVIRONMENTAL MICROBIOLOGY, Issue 9 2008Elodie Foulon Summary Very few studies have analysed the niches of pelagic protist in details. This is because for most protists, both an accurate species definition and methods for routine detection and quantification of cells are lacking. The morphospecies Micromonas pusilla, a marine unicellular green alga, is the most ubiquitous and cosmopolitan picoeukaryote described to date. This species comprises several independent genetic lineages or clades, which are not currently distinguishable based on comparison of their morphology or biogeographical distribution. Molecular probes were used to detect and quantify the genetic clades of M. pusilla in samples from temperate, polar and tropical environments in order to assess potential ecological niche partitioning. The three clades were detected in all biogeographical regions studied and were commonly found in sympatry. Cell abundances recorded for clades A and B were high, especially at coastal stations. Clade C, when detected, was always at low abundances and is suggested to be a low-light clade. Shifts in the contribution of clades to total M. pusilla abundance were observed along environmental gradients, both at local and basin-wide scales. This suggests that the phylogenetic clades occupy specific niches and confirms the existence of cryptic species within the morphospecies M. pusilla. Parameters which can precisely explain the distribution of these cryptic species remain to be elucidated. [source] Patterns of bacterial diversity across a range of Antarctic terrestrial habitatsENVIRONMENTAL MICROBIOLOGY, Issue 11 2007Etienne Yergeau Summary Although soil-borne bacteria represent the world's greatest source of biological diversity, it is not well understood whether extreme environmental conditions, such as those found in Antarctic habitats, result in reduced soil-borne microbial diversity. To address this issue, patterns of bacterial diversity were studied in soils sampled along a > 3200 km southern polar transect spanning a gradient of increased climate severity over 27° of latitude. Vegetated and fell-field plots were sampled at the Falkland (51°S), South Georgia (54°S), Signy (60°S) and Anchorage Islands (67°S), while bare frost-sorted soil polygons were examined at Fossil Bluff (71°S), Mars Oasis (72°S), Coal Nunatak (72°S) and the Ellsworth Mountains (78°S). Bacterial 16S rRNA gene sequences were recovered subsequent to direct DNA extraction from soil, polymerase chain reaction amplification and cloning. Although bacterial diversity was observed to decline with increased latitude, habitat-specific patterns appeared to also be important. Namely, a negative relationship was found between bacterial diversity and latitude for fell-field soils, but no such pattern was observed for vegetated sites. The Mars Oasis site, previously identified as a biodiversity hotspot within this region, proved exceptional within the study transect, with unusually high bacterial diversity. In independent analyses, geographical distance and vegetation cover were found to significantly influence bacterial community composition. These results provide insight into the factors shaping the composition of bacterial communities in Antarctic terrestrial habitats and support the notion that bacterial diversity declines with increased climatic severity. [source] Technical basis for polar and nonpolar narcotic chemicals and polycyclic aromatic hydrocarbon criteria.ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 7 2009Abstract A method is presented for extending the target lipid model (TLM) of narcotic toxicity to polar narcotic chemicals. The proposed polyparameter TLM extends the applicability of the TLM by including polar compounds and removing explicit chemical class corrections. The validity of the model is tested using a data set of 1,687 acute toxicity tests for 42 aquatic species, including fish, amphibians, arthropods, mollusks, polychaetes, coelenterates, protozoans, and algae, and 398 chemicals. The target lipid-water partition coefficient is computed using the Abraham polyparameter model. This replaces use of the octanol-water partition coefficient so that the partitioning of polar narcotic chemicals can be described correctly. The model predicts the log median lethal concentration with a root mean square error of 0.460 for nonpolar and polar chemicals and 0.501 for only polar chemicals. [source] Multiple computer-automated structure evaluation study of aquatic toxicity.ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2003Abstract An acute toxicity model was constructed on the basis of 901 chemicals tested for toxicity against the luminescent bacteria Vibrio fischeri (formerly Photobacterium phosphoreum, the Microtox® test). The model was created using the Multiple Computer-Automated Structure Evaluation (M-CASE) program. The model can correctly predict acute toxicity for 92% of the compounds with an error averaging 0.55 log units per median effect concentration (EC50). The main toxicophores, corresponding to polar and nonpolar narcosis, and other types of reactive chemicals were identified. [source] Biotransformation of n -hexadecane by cell suspension cultures of Cinchona robusta and Dioscorea compositaENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2001Carolina Vega-Jarquin Abstract This manuscript evaluates the phytotoxicity and biotransformation of n -hexadecane as well as peroxidase activity and cytochrome P450 concentration in microsomes for cell suspension cultures of Cinchona robusta and Dioscorea composita. Phytotoxicity was evaluated based on viability and growth. Cell cultures were exposed to a 2 and 4% (v/v) dose of n -hexadecane. The biotransformation of n -hexadecane was determined based on labeled recovery in polar, nonpolar, and cell residue fractions after cell culture extraction during exponential cell growth phase and stationary phase. Differences were observed in accumulation of label during cell growth phase and stationary phase for the cells of the two plants. Differences also were observed between phases for label in polar and nonpolar fractions. Thin-layer chromatography determined labeled intermediates and some were identified. The activity of peroxidase and concentration of cytochrome P450 was lower in C. robusta than in controls and greater in D. composita than in controls. In vitro biotransformation was not successful. [source] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||