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Selected AbstractsThe Synthesis of the Dimethyl Ester of Quino[4,4a,5,6- efg]-Annulated 7-Demethyl-8-deethylmesoporphyrin and Three of Its Isomers with Unprecedented peri -Condensed Quinoline Porphyrin Structures.EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2004Molecules with Outstanding Properties as Sensitizers for Photodynamic Therapy in the Far-Red Region of the Visible Spectrum Abstract The mesoporphyrin dimethyl ester nickel complex has been formylated via the Vilsmeier method. The four possible mono meso-formyl derivatives were isolated and characterized. Wadsworth,Emmons coupling with the anion of (diethylphosphono)acetonitrile converted these aldehydes into the four novel meso acrylonitriles. Brief treatment of these acrylonitrile systems in hot trichloroacetic acid resulted in the formation of four achiral porphyrin derivatives with unprecedented nickel complexes of quino-fused porphyrins. Subsequent removal of the nickel gave four quino-porphyrin free bases: quino[4,4a,5,6- efg]-annulated 7-demethyl-8-deethylmesoporphyrin dimethyl ester 6a, 2,-(methoxycarbonyl)quino[4,4a,5,6- jkl]-annulated 12-demethyl-13-de[2,-(methoxycarbonyl)ethyl]mesoporphyrin dimethyl ester 6b, 2,-(methoxycarbonyl)quino[4,4a,5,6- qrs]-annulated 18-demethyl-17-de(2,-methoxycarbonylethyl)mesoporphyrin dimethyl ester 6c and quino[4,5,6,7- abt]-annulated 2-demethyl-3-deethylmesoporphyrin dimethyl ester 6d. The structures of these systems were unambiguously determined via mass spectroscopy and a plethora of NMR techniques. In the same way, etioporphyrin and octaethylporphyrin were converted into the corresponding peri -condensed quinoporphyrins as products, which shows that the formation of novel pericondensed quino-porphyrins is a general reaction in the porphyrin series and will have a wide scope in this field. Also, a plausible reaction mechanism for the formation of the quinoporphyrin systems was derived. As a first test for the use of these systems as sensitizers in far-red phototherapy, the quantum yield of singlet oxygen generation by 6a in toluene was studied. This quantum yield is 0.77, which is even higher than the singlet oxygen generation by sensitized meso-tetraphenylporphyrin. Secondly, when Chinese Hamster ovary (CHO) cells were incubated in medium which contained up to 15 ,g/ml of 6a, the survival rate of the cells in the dark is complete within experimental error, showing that under these conditions, 6a is not toxic to CHO cells. When CHO cells incubated in medium containing 6a in concentrations of 1 ,g/ml and higher were treated with white light of intensity 30 mW/cm2 for 15 minutes, complete cell death was observed. Based on these facts, we expect that all four achiral systems will show very promising properties to form the basis of a photodynamic therapy in far-red light. The fact that these systems are achiral is an additional bonus for medical applications. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Triplet Exciton and Polaron Dynamics in Phosphorescent Dye Blended Polymer Photovoltaic DevicesADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Chang-Lyoul Lee Abstract The triplet exciton and polaron dynamics in phosphorescent dye (PtOEP) blended polymer (MEH-PPV) photovoltaic devices are investigated by quasi-steady-state photo-induced absorption (PIA) spectroscopy. According to the low-temperature PIA and photoluminescence (PL) results, the increase in strength of the triplet-triplet (T1 - Tn) absorption of MEH-PPV in the blend system originates from the triplet-triplet energy transfer from PtOEP to MEH-PPV. The PtOEP blended MEH-PPV/C60 bilayer photovoltaic device shows a roughly 30%,40% enhancement in photocurrent and power-conversion efficiency compared to the device without PtOEP. However, in contrast to the bilayer device results, the bulk heterojunction photovoltaic devices do not show a noticeable change in photocurrent and power-conversion efficiency in the presence of PtOEP. The PIA intensity, originating from the polaron state, is only slightly higher (within the experimental error), indicating that carrier generation in the bulk heterojunction is not enhanced in the presence of PtOEP. The rate and probability of the exciton dissociation between PtOEP and PCBM is much faster and higher than that of the triplet-triplet energy transfer between PtOEP and MEH-PPV. [source] Recombinant human glucose-6-phosphate dehydrogenaseFEBS JOURNAL, Issue 14 2002Evidence for a rapid-equilibrium random-order mechanism Cloning and over-expression of human glucose 6-phosphate dehydrogenase (Glc6P dehydrogenase) has for the first time allowed a detailed kinetic study of a preparation that is genetically homogeneous and in which all the protein molecules are of identical age. The steady-state kinetics of the recombinant enzyme, studied by fluorimetric initial-rate measurements, gave converging linear Lineweaver,Burk plots as expected for a ternary-complex mechanism. Patterns of product and dead-end inhibition indicated that the enzyme can bind NADP+ and Glc6P separately to form binary complexes, suggesting a random-order mechanism. The Kd value for the binding of NADP+ measured by titration of protein fluorescence is 8.0 µm, close to the value of 6.8 µm calculated from the kinetic data on the assumption of a rapid-equilibrium random-order mechanism. Strong evidence for this mechanism and against either of the compulsory-order possibilities is provided by repeating the kinetic analysis with each of the natural substrates replaced in turn by structural analogues. A full kinetic analysis was carried out with deaminoNADP+ and with deoxyglucose 6-phosphate as the alternative substrates. In each case the calculated dissociation constant upon switching a substrate in a random-order mechanism (e.g. that for NADP+ upon changing the sugar phosphate) was indeed constant within experimental error as expected. The calculated rate constants for binding of the leading substrate in a compulsory-order mechanism, however, did not remain constant when the putative second substrate was changed. Previous workers, using enzyme from pooled blood, have variously proposed either compulsory-order or random-order mechanisms. Our study appears to provide unambiguous evidence for the latter pattern of substrate binding. [source] Silicon-Doped LiFePO4 Single Crystals: Growth, Conductivity Behavior, and DiffusivityADVANCED FUNCTIONAL MATERIALS, Issue 11 2009Ruhul Amin Abstract Single crystals of silicon doped LiFePO4 with a silicon content of 1% are grown successfully by the floating zone technique and characterized by single-crystal and powder X-ray diffraction, secondary ion mass spectroscopy, and chemical analysis. Electron paramagnetic resonance demonstrates the presence of only Fe2+; no traces of Fe3+ are found. Impedance spectroscopy as well as step-function polarization/depolarization (DC) measurements are carried out using the cells Ti/LiFe(Si)PO4/Ti and LiAl/LiI/LiFe(Si)PO4/LiI/LiAl. The electronic and ionic conductivities as well as the Li-diffusivity of the sample in the major crystallographic directions ([h00], [0k0], and [00l]) are determined. Within experimental error the transport properties along the b- and c-axes are found to be the same but differ significantly from the a-axis, which exhibits lower values. Compared to undoped LiFePO4, Si-doping leads to an increase of the ionic conductivity while the electronic conductivity decreases, which is in agreement with a donor effect. The activation energies of conductivities and diffusivities are interpreted in terms of defect chemistry and relevant Brouwer diagrams are given. [source] Geoelectric dimensionality in complex geological areas: application to the Spanish Betic ChainGEOPHYSICAL JOURNAL INTERNATIONAL, Issue 3 2004Anna Martí SUMMARY Rotational invariants of the magnetotelluric impedance tensor may be used to obtain information on the geometry of underlying geological structures. The set of invariants proposed by Weaver et al. (2000) allows the determination of a suitable dimensionality for the modelling of observed data. The application of the invariants to real data must take into account the errors in the data and also the fact that geoelectric structures in the Earth will not exactly fit 1-D, 2-D or simple 3-D models. In this work we propose a method to estimate the dimensionality of geoelectric structures based on the rotational invariants, bearing in mind the experimental error of real data. A data set from the Betic Chain (Spain) is considered. We compare the errors of the invariants estimated by different approaches: classical error propagation, generation of random Gaussian noise and bootstrap resampling, and we investigate the matter of the threshold value to be used in the determination of dimensionality. We conclude that the errors of the invariants can be properly estimated by classical error propagation, but the generation of random values is better to ensure stability in the errors of strike direction and distortion parameters. The use of a threshold value between 0.1 and 0.15 is recommended for real data of medium to high quality. The results for the Betic Chain show that the general behaviour is 3-D with a disposition of 2-D structures, which may be correlated with the nature of the crust of the region. [source] Densification of Oxide Nanoparticle Thin Films by Irradiation with Visible LightADVANCED FUNCTIONAL MATERIALS, Issue 8 2009Massimo F. Bertino Abstract A technique is presented that allows for altering of the physical characteristics of films of TiO2 nanoparticles by exposure to visible light. In this technique, dye-sensitized oxide nanoparticles are deposited on a substrate by dip-coating. Photodissociation of the organic ligand layer leads to cross-linking of the nanoparticles. Consequently, irradiated films have a decreased porosity, an increased index of refraction and an increased hydrophobicity. Films irradiated with green light are compared to films irradiated with UV light. Within experimental error, visible- and UV-illumination induces the same changes in the films. The mechanism of surfactant elimination in dye-sensitized oxide particles is discussed, patterning is demonstrated, and prospective applications of the technique are considered. [source] Air temperature effect on spray evaporation in sprinkler irrigation,IRRIGATION AND DRAINAGE, Issue 4 2002Dr Giulio Lorenzini évaporation aérienne; irrigation par arroseur; équipement expérimental Abstract The temperature effect of the surrounding environment on mean steady aerial water evaporation in sprinkler irrigation is investigated. An experimental set-up was designed and built to work at opportune operating conditions holding all the other variables constant to minimise the experimental error. One hundred and thirty-seven tests were performed for this work, of which 81 were considered valid for a statistical analysis of the data measured. Evaporation ranged from 4.15 to 7.73% as the air temperature varied from 21.0 to 27.0° C. Results show a clear dependence of sprinkler water evaporation on air temperature with a logarithmic relation. Further investigations will examine broader temperature intervals to improve the assessment and will consider the effects due to other parameters affecting the phenomenon. Copyright © 2002 John Wiley & Sons, Ltd. Résumé Les effets de la température de l'environnement sur l'irrigation par arroseur ont été examinés. Un eq,uipement expérimental a été conçu et créé pour fonctionner dans des conditions d'emploi propices, et on a travaillé aussi pour tenir les autres variables le plus possible constantes pour minimiser l'erreur expérimentale. On a réalisé 137 tests et seulement 81 ont été considérés bons pour l'analyse statistique. On a vu que l'évaporation change de 4.15 à 7.73 pour cent avec le changement de température de 21.0 à 27.0° C. Les résultats montrent une claire dépendance logarithmique de l'évaporation avec la température de l'air. On propose dans le futur d'étendre l'intervalle des températures pour confirmer les résultats déjà vus et aussi de tester les influences d'autres variables d'intérêt pour ce phénomène. Copyright © 2002 John Wiley & Sons, Ltd. [source] A comparative study of single-line and Rietveld strain,size evaluation procedures using MgO ceramicsJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 2 2002Suminar Pratapa Strain,size evaluations from diffraction line broadening for MgO ceramic materials have been compared using single-line integral-breadth and Rietveld procedures with the Voigt function. Diffraction data were measured by Bragg,Brentano X-ray diffractometry (XRD), without incident beam monochromatization, and neutron diffractometry (ND) to encompass near-surface and bulk effects, respectively. The specimens consisted of sets of MgO ceramics and MgO,Y2O3 ceramic composites sintered over a range of temperatures. An MgO ceramic sintered at 1723,K for 2,h exhibited slightly less XRD broadening than the standard LaB6 NIST 660 SRM, and was therefore selected to make instrument profile corrections for both XRD and ND data. It was found for both data types that: (a) sintering initially relieves residual strain present in the MgO powder used to sinter the ceramics and also promotes grain growth; (b) residual strain of the MgO ceramic minimizes as the sintering temperature increases, and then increases with further rise in the sintering temperature, presumably as a result of intragranular interactions associated with grain growth; and (c) introduction of the second phase (Y2O3) increases strain and inhibits crystal growth. The single-line and Rietveld methods gave similar strain values from both the XRD and ND data within the limits of experimental error, but there were substantial differences between the single-line and Rietveld size estimates determined with the XRD and ND data. [source] Use of microemulsions for removal of color and dyes from textile wastewaterJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 6 2004Tereza Neuma de Castro Dantas Abstract One of the major environmental problems in the textile dyeing industry is the removal of color from effluents. The present study deals with color removal from effluents using microemulsions. The wastewater used in this study was the reactive exhausted dye liquor from a dyeing house containing Procion Yellow H-E4R (CI Reactive Yellow 84), Procion Blue H-ERD (CI Reactive Blue 160) and Procion Red H-E3B (CI Reactive Red 120). Color removal was determined by CIEL*a*b* (CIELAB) color space, CIEL*a*b* color difference, ,E*ab, and absorbance. Color removal greater than 95% was achieved, attaining values lower than the consent requirements established by the Environmental Agency. It was observed that pH is an important parameter in color removal and effluent pH correction from 10.44 to 9 before extraction improved results. The results obtained were modeled using the Scheffé net method and evaluated through the construction of isoresponse diagrams by correlation graphics between experimental values and those obtained through use of model equations, providing an experimental error of less than 2%. The optimized method very efficiently removed all dyes contained in the effluent. The same microemulsion phase recovered after the extraction process can be used at least a further 14 times and all the extractions gave good color removal. Copyright © 2004 Society of Chemical Industry [source] Gas-phase basicities for ions from bradykinin and its des-arginine analoguesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 8 2001Nigel P. Ewing Abstract Apparent gas-phase basicities (GBapps) for [M + H]+ of bradykinin, des-Arg1 -bradykinin and des-Arg9 -bradykinin have been assigned by deprotonation reactions of [M + 2H]2+ in a Fourier transform ion cyclotron resonance mass spectrometer. With a GBapp of 225.8 ± 4.2 kcal mol,1, bradykinin [M + H]+ is the most basic of the ions studied. Ions from des-Arg1 -bradykinin and des-Arg9 -bradykinin have GBapp values of 222.8 ± 4.3 kcal mol,1 and 214.9 ± 2.3 kcal mol,1, respectively. One purpose of this work was to determine a suitable reaction efficiency ,break point' for assigning GBapp values to peptide ions using the bracketing method. An efficiency value of 0.1 (i.e. approximately 10% of all collisions resulting in a deprotonation reaction) was used to assign GBapps. Support for this criterion is provided by the fact that our GBapp values for des-Arg1 -bradykinin and des-Arg9 -bradykinin are identical, within experimental error, to literature values obtained using a modified kinetic method. However, the GBapps for bradykinin ions from the two studies differ by 10.3 kcal mol,1. The reason for this is not clear, but may involve conformation differences produced by experimental conditions. The results may be influenced by salt-bridge conformers and/or by conformational changes caused by the use of a proton-bound heterodimer in the kinetic method. Factors affecting the basicities of these peptide ions are also discussed, and molecular modeling is used to provide information on protonation sites and conformations. The presence of two highly basic arginine residues on bradykinin results in its high GBapp, while the basicity of des-Arg1 -bradykinin ions is increased by the presence of two proline residues at the N-terminus. The proline residue in the second position folds the peptide chain in a manner that increases intramolecular hydrogen bonding to the protonated N-terminal amino group of the proline at the first position. Copyright © 2001 John Wiley & Sons, Ltd. [source] Determination of the electron affinities of ,- and ,-naphthyl radicals using the kinetic method with full entropy analysis.JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 6 2001H bond dissociation energies of naphthalene, The C Abstract The C , H bond dissociation energies for naphthalene were determined using a negative ion thermochemical cycle involving the gas-phase acidity (,Hacid) and electron affinity (EA) for both the ,- and ,-positions. The gas-phase acidity of the naphthalene ,- and ,-positions and the EAs of the ,- and ,-naphthyl radicals were measured in the gas phase in a flowing afterglow,triple quadrupole apparatus. A variation of the Cooks kinetic method was used to measure the EAs of the naphthyl radicals by collision-induced dissociation of the corresponding ,- and ,-naphthylsulfinate adducts formed by reactions in the flow tube portion of the instrument. Calibration references included both , and , radicals, and full entropy analysis was performed over a series of calibration curves measured at collision energies ranging from 3.5 to 8 eV (center-of-mass). The measured EAs are 33.0 ± 1.4 and 31.4 ± 1.0 kcal mol,1 (1 kcal = 4.184 kJ) for the ,- and ,-naphthyl radicals, respectively. The gas-phase acidities for naphthalene were measured by the DePuy silane cleavage method, which utilizes the relative abundances of aryldimethylsiloxides and trimethylsiloxide that result from competitive cleavages from a proposed pentacoordinate hydroxysiliconate intermediate. The measured acidities are 394.0 ± 5.0 and 397.6 ± 4.8 kcal mol,1 for the ,- and ,- positions, respectively. The C , H bond dissociation energies calculated from the thermochemical cycle are 113.4 ± 5.2 and 115.4 ± 4.9 kcal mol,1 for the ,- and ,-positions, respectively. These energies are, to within experimental error, indistinguishable and are approximately the same as the first bond dissociation energy for benzene. Copyright © 2001 John Wiley & Sons, Ltd. [source] Added nitrogen interaction as affected by soil nitrogen pool size and fertilization , significance of displacement of fixed ammoniumJOURNAL OF PLANT NUTRITION AND SOIL SCIENCE, Issue 2 2004Shan Lin Abstract Displacement of NH4+ fixed in clay minerals by fertilizer 15NH4+ is seen as one mechanism of apparent added nitrogen interactions (ANI), which may cause errors in 15N tracer studies. Pot and incubation experiments were carried out for a study of displacement of fixed NH4+ by 15N-labeled fertilizer (ammonium sulfate and urea). A typical ANI was observed when 15N-labeled urea was applied to wheat grown on soils with different N reserves that resulted from their long-term fertilization history: Plants took up more soil N when receiving fertilizer. Furthermore, an increased uptake of 15N-labeled fertilizer, induced by increasing unlabeled soil nitrogen supply, was found. This ANI-like effect was in the same order of magnitude as the observed ANI. All causes of apparent or real ANI can be excluded as explanation for this effect. Plant N uptake-related processes beyond current concepts of ANI may be responsible. NH4+ fixation of fertilizer 15NH4+ in sterilized or non-sterile, moist soil was immediate and strongly dependent on the rate of fertilizer added. But for the tested range of 20 to 160 mg 15NH4+ -N kg,1, the NH4+ fixation rate was low, accounting for only up to 1.3,% of fertilizer N added. For sterilized soil, no re-mobilization of fixed 15NH4+ was observed, while in non-sterile, biologically active soil, 50,% of the initially fixed 15NH4+ was released up to day 35. Re-mobilization of 15NH4+ from the pool of fixed NH4+ started after complete nitrification of all extractable NH4+. Our results indicate that in most cases, experimental error from apparent ANI caused by displacement of fixed NH4+ in clay is unlikely. In addition to the low percentage of only 1.3,% of applied 15N, present in the pool of fixed NH4+ after 35 days, there were no indications for a real exchange (displacement) of fixed NH4+ by 15N. Einfluss der Düngung und des N-Bodenvorrats auf Added Nitrogen Interactions , Bedeutung des Ersatzaustauschs mit in Tonmineralen fixiertem Ammonium Ersatzaustausch (displacement) von in Tonmineralen fixiertem NH4+ durch Dünger- 15NH4+ gilt als eine Ursache für scheinbare (apparente) Added Nitrogen Interactions (ANI). Diese werden als Fehlerursache in 15N-Tracerstudien diskutiert. Durch Einsatz von 15N-markiertem Ammoniumsulfat und Harnstoff wurde in Inkubations- und Gefäßversuchen geprüft, welche Bedeutung der Ersatzaustausch von gedüngtem 15NH4+ mit in Tonmineralen fixiertem Ammonium hat. Mit zwei Böden, die sich nur in ihrer Düngungsgeschichte unterschieden, zeigte sich nach Düngung mit 15N-markiertem Harnstoff zu Weizen eine typische ANI: Nach Düngung nahmen die Pflanzen nicht nur Dünger-N, sondern auch mehr Boden-N auf. Zusätzlich zeigte sich, dass die Pflanzen bei gleicher Düngung mehr Dünger-N aufnahmen, wenn sie auf Boden mit größerem N-Vorrat wuchsen. Beide Effekte hatten die gleiche Größenordnung. Dieser Befund kann mit den bisher beschriebenen Ursachen für ANI nicht erklärt werden. Wahrscheinlicher scheint eine Beeinflussung der aktiven, pflanzlichen N-Aufnahme. Die Fixierung von Dünger- 15NH4+ in sterilisiertem oder nicht sterilisiertem, frischem Boden erfolgte unmittelbar und hing von der gedüngten N-Menge ab. Innerhalb des untersuchten Bereichs von 20 bis 160 mg 15NH4+ -N kg,1 wurden nur 1,3,% des gedüngten NH4+ in Tonmineralen fixiert. Dieses fixierte NH4+ wurde bei zuvor sterilisiertem Boden nicht wieder freigesetzt. Hingegen wurden aus den Tonmineralen des biologisch aktiven, nicht sterilisierten Bodens innerhalb des 35-tägigen Versuchszeitraums 50,% des fixierten NH4+ wieder freigesetzt. Diese Freisetzung setzte in dem Moment ein, als der Vorrat des leicht verfügbaren, 2 M KCl-extrahierbaren NH4+ durch Nitrifikation vollständig erschöpft war. Unsere Ergebnisse zeigen, dass Versuchsfehler durch Ersatzaustausch mit Tonmineral-fixiertem Ammonium als Ursache für die scheinbare ANI in den meisten Fällen auszuschließen sein dürften. Innerhalb von 35 Tagen traten maximal 1,3,% des gedüngten 15N-markierten Dünger-N in die Fraktion des fixierten Ammoniums über. Hinweise für einen echten Ersatzaustausch des in Tonmineralen fixierten Ammoniums durch Dünger-N konnten nicht gefunden werden. [source] Liquidus Prediction in Multicomponent Lithium Alumosilicate GlassesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 4 2008Lothar Wondraczek An empirical nine-parameter linear mixing model was developed to estimate the liquidus temperature of zirconia-bearing technical lithium alumosilicate glasses that contain up to 12 major components. The model covers glasses that are suitable as precursor glasses for ,-quartz or ,-spodumene-type glass ceramics with low coefficients of thermal expansion. Molar coefficients of liquidus temperatures are provided for each component. A self-consistency test results in a standard deviation between predicted and measured liquidus temperatures of 7.5°C, within a range of approximately 200°C and for a typical experimental error of 10°C. [source] Refractive Index Drop Observed After Precision Molding of Optical Elements: A Quantitative Understanding Based on the Tool,Narayanaswamy,Moynihan ModelJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 3 2008Ulrich Fotheringham The room-temperature refractive index is measured for three different prior cooling rates (approximately 10, 50, and 250 K/h) for two glasses especially developed for precision molding. The empirical logarithmic relationship between the cooling rate and the refractive index is also reproduced for the comparatively high cooling rate of ca. 250 K/h. The same relationship is found in a simulation of these cooling rates by the semiempirical Tool,Narayanaswamy,Moynihan model for structural relaxation, with the necessary parameters obtained from differential scanning calorimetry and temperature jump experiments. The measured and the simulated refractive indices coincide within the limits of experimental error. The results demonstrate that the index drop, which is observed when these glasses are first cooled at a regular optical cooling rate (e.g., 2 K/h), and then precision molded (typical cooling rate 1000 K/h), can be understood considering the concepts of structural relaxation. [source] Substrate inhibition of Pediococcus acidilactici by glucose on a waste medium.LETTERS IN APPLIED MICROBIOLOGY, Issue 5 2003Simulations, experimental results Abstract Aims: The possibility of substrate inhibition by glucose on biomass and pediocin production was studied in cultures of Pediococcus acidilactici on a residual medium. Methods and Results: Calculation of the substrate inhibition coefficient in the context of microbial growth is generally laborious, and very prone to experimental error. However, a simulation combining logistic and Monod kinetics equations demonstrates that quantitative evidence for this type of inhibition, without the possibility of misinterpretation, can be obtained through the comparison of punctual preasymptotic productions as a function of substrate concentration. Significance and Impact of the Study: It was concluded that glucose had an inhibitory effect on growth, but not on bacteriocin production. [source] Model Development in Thermal Styrene PolymerizationMACROMOLECULAR SYMPOSIA, Issue 1 2007Bryan Matthews Abstract Summary: The thermal polymerization of styrene is usually modeled by relying on a reaction scheme and a set of equations that were developed more than three decades ago by Hui and Hamielec. Many detailed models of styrene polymerization are available in the open literature and they are mostly based on the work of Hui and Hamielec, which nearly makes this the standard to follow in explaining the behavior of polystyrene reactors. The model of Hui and Hamielec does a very nice job of describing monomer conversion data but discrepancies are seen between observed and predicted values of number and weight average molecular weights, Mn and Mw. Discrepancies in number average molecular weight seem to be the result of random noise. Discrepancies in weight average molecular weight grow as the polymerization temperature decreases and some of the trends observed in the residuals over the entire temperature range cannot be attributed to random noise. Hui and Hamielec attributed the observed deficiencies to a standard deviation of ±10% in their GPC measurements. A new data set with an experimental error of 2% for average molecular weights is presented. The set contains measured values of Mn, Mw and Mz, so the polymerization scheme has been extended to include third order moments. The data set also includes the effect of ethylbenzene as a chain transfer agent. We present the results of comparing model predictions to our measurements and the adjustments made in the original set of kinetic parameters published by Hui and Hamielec. [source] Free Radical Bulk Polymerization of Styrene: Simulation of Molecular Weight Distributions to High Conversion Using Experimentally Obtained Rate CoefficientsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 6 2003Per B. Zetterlund Abstract Previously obtained experimental conversion-dependences of the propagation rate coefficient (kp), the termination rate coefficient (kt) and the initiator efficiency (f) for the free-radical bulk polymerization of styrene at 70,°C have been used to simulate the full molecular weight distributions (MWD) to high conversion using the software package PREDICI, providing a robust test of the kinetic model adopted. Satisfactory agreement with the experimental MWD's (GPC) was obtained up to approximately 70% conversion. Beyond 70% conversion, the high MW shoulder that appears was correctly predicted, although the amount of such polymer was somewhat underestimated. This discrepancy is believed to probably have its origin in experimental error in the conversion-dependences of kp, kt and f, in particular kt, that were employed in the simulations, rather than indicate a more fundamental short-coming of the model employed. [source] Solid-state 1H , 19F/19F , 1H CP/MAS NMR study of poly(vinylidene fluoride)MAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2002Shinji Ando Abstract Solid-state 1H , 19F and 19F , 1H cross-polarization magic angle spinning (CP/MAS) NMR spectra have been investigated for a semicrystalline fluoropolymer, namely poly(vinylidene fluoride) (PVDF). The 1H , 19F CP/MAS spectra can be fitted by five Lorentzian functions, and the amorphous peaks were selectively observed by the DIVAM CP pulse sequences. Solid-state spin-lock experiments showed significant differences in T1,F and T1,H between the crystalline and amorphous domains, and the effective time constants, THF* and T1,*, which were estimated from the 1H , 19F CP curves, also clarify the difference in the strengths of dipolar interactions. Heteronuclear dipolar oscillation behaviour is observed in both standard CP and 1H , 19F inversion recovery CP (IRCP) experiments. The inverse 19F , 1H CP-MAS and 1H , 19F CP-drain MAS experiments gave complementary information to the standard 1H , 19F CP/MAS spectra in a manner reported in our previous papers for other fluoropolymers. The value of NF/NH (where N is a spin density) estimated from the CP-drain curve is within experimental error equal to unity, which is consistent with the chemical structure. Copyright © 2001 John Wiley & Sons, Ltd. [source] Estimation of Carboxylic Acid Ester Hydrolysis Rate ConstantsMOLECULAR INFORMATICS, Issue 9-10 2003H. Hilal Abstract SPARC chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid esters from molecular structure. The energy differences between the initial state and the transition state for a molecule of interest are factored into internal and external mechanistic perturbation components. The internal perturbations quantify the interactions of the appended perturber (P) with the reaction center (C). These internal perturbations are factored into SPARC's mechanistic components of electrostatic and resonance effects. External perturbations quantify the solute-solvent interactions and are factored into H-bonding, field stabilization and steric effects. These models have been tested using 1471 measured hydrolysis rate constants in water and mixed-solvent systems at different temperatures. The aggregate RMS deviation of the calculated versus observed values was 0.374,M,1s,1; close to the intralaboratory experimental error. [source] Differential analysis of DNA microarray gene expression dataMOLECULAR MICROBIOLOGY, Issue 4 2003G. Wesley Hatfield Summary Here, we review briefly the sources of experimental and biological variance that affect the interpretation of high-dimensional DNA microarray experiments. We discuss methods using a regularized t -test based on a Bayesian statistical framework that allow the identification of differentially regulated genes with a higher level of confidence than a simple t -test when only a few experimental replicates are available. We also describe a computational method for calculating the global false-positive and false-negative levels inherent in a DNA microarray data set. This method provides a probability of differential expression for each gene based on experiment-wide false-positive and -negative levels driven by experimental error and biological variance. [source] Improving the precision of cotton performance trials conducted on highly variable soils of the southeastern USA coastal plainPLANT BREEDING, Issue 6 2007B. T. Campbell Abstract Reliable agronomic and fibre quality data generated in Upland cotton (Gossypium hirsutum L.) cultivar performance trials are highly valuable. The most common strategy used to generate reliable performance trial data uses experimental design to minimize experimental error resulting from spatial variability. However, an alternative strategy uses a posteriori statistical procedures to account for spatial variability. In this study, the efficiency of the randomized complete block (RCB) design and nearest neighbour adjustment (NNA) were compared in a series of cotton performance trials conducted in the southeastern USA to identify the efficiency of each in minimizing experimental error for yield, yield components and fibre quality. In comparison to the RCB, relative efficiency of the NNA procedure varied amongst traits and trials. Results show that experimental analyses, depending on the trait and selection intensity employed, can affect cultivar or experimental line selections. Based on this study, we recommend researchers conducting cotton performance trials on variable soils consider using NNA or other spatial methods to improve trial precision. [source] Kevlar and glass fiber treatment for thermoplastic composites by step polycondensationPOLYMER COMPOSITES, Issue 3 2007H. Salehi-Mobarakeh Nylon-6,6 was grafted at the surface of glass and plasma-treated Kevlar fibers for use in nylon,Kevlar thermoplastic composites. Hydroxyl and, in the case of Kevlar, amine end-groups occur at the fibre surface, either as defects or due to the plasma treatment. These were used as anchor points for nylon-6,6 step polycondensation. Fibers were subjected to successive dipping in adipoyl chloride/CH2Cl2 and aqueous hexamethylenediamine solutions in order to attach and grow high molecular weight polymer on the fiber surface. Grafted nylon was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, differential scanning calorimetry and thermogravimetry. It was shown that no backbiting occurred during the first stage of the grafting process and that the polymer quantity increased linearly with number of passes, up to ,50 passes for plasma-treated Kevlar and 100 for glass fibers, after which polymer quantity remained constant, within experimental error, which was attributed to the onset of termination reactions. POLYM. COMPOS., 28:278,286, 2007. © 2007 Society of Plastics Engineers [source] Experimental testing of a random medium optical model of porous silicon for photovoltaic applicationsPROGRESS IN PHOTOVOLTAICS: RESEARCH & APPLICATIONS, Issue 1 2001A. A. Abouelsaood We have developed a model for light propagation in porous silicon (PS) based on the theory of wave propagation in random media. The low porosity case is considered, with silicon being the host material assuming randomly distributed spherical voids as scattering particles. The specular and the diffuse part of the light could be determined and treated separately. The model is applied to the case in which porous silicon would be used as a diffuse back reflector in a thin-film crystalline silicon solar cell realized in an ultrathin (1,3,,m) epitaxially grown Si layer on PS. Three,layer structures (epi/PS/Si) have been fabricated by atmospheric pressure chemical vapor deposition (APCVD) of 150,1000 nm epitaxial silicon layers on silicon wafers of which 150,450 nm of the surface has been electrochemically etched. An excellent agreement is found between the experimentally measured reflection data in the 400,1000 nm wavelength range and those calculated using the proposed model. The values of the layer thickness agree, within a reasonable experimental error, with those obtained independently by cross,sectional transmission electron microscopy (XTEM) analysis. This provides an experimental verification of the random,medium approach to porous silicon in the low porosity case. The analysis shows that the epitaxial growth process has led to appreciable porosity decrease of an initially high,porosity layer from about 60% to 20,30%. Copyright © 2001 John Wiley & Sons, Ltd. [source] Mining protein dynamics from sets of crystal structures using "consensus structures"PROTEIN SCIENCE, Issue 4 2010Gerard J. P. van Westen Abstract In this work, we describe two novel approaches to utilize the dynamic structure information implicitly contained in large crystal structure data sets. The first approach visualizes both consistent as well as variable ligand-induced changes in ligand-bound compared with apo protein crystal structures. For this purpose, information was mined from B-factors and ligand-induced residue displacements in multiple crystal structures, minimizing experimental error and noise. With this approach, the mechanism of action of non-nucleoside reverse transcriptase inhibitors (NNRTIs) as an inseparable combination of distortion of protein dynamics and conformational changes of HIV-1 reverse transcriptase was corroborated (a combination of the previously proposed "molecular arthritis" and "distorted site" mechanisms). The second approach presented here uses "consensus structures" to map common binding features that are present in a set of structures of NNRTI-bound HIV-1 reverse transcriptase. Consensus structures are based on different levels of structural overlap of multiple crystal structures and are used to analyze protein,ligand interactions. The structures are shown to yield information about conserved hydrogen bonding interactions as well as binding-pocket flexibility, shape, and volume. From the consensus structures, a common wild type NNRTI binding pocket emerges. Furthermore, we were able to identify a conserved backbone hydrogen bond acceptor at P236 and a novel hydrophobic subpocket, which are not yet utilized by current drugs. Our methods introduced here reinterpret the atom information and make use of the data variability by using multiple structures, complementing classical 3D structural information of single structures. [source] Probabilistic cross-link analysis and experiment planning for high-throughput elucidation of protein structurePROTEIN SCIENCE, Issue 12 2004Xiaoduan Ye Abstract Emerging high-throughput techniques for the characterization of protein and protein-complex structures yield noisy data with sparse information content, placing a significant burden on computation to properly interpret the experimental data. One such technique uses cross-linking (chemical or by cysteine oxidation) to confirm or select among proposed structural models (e.g., from fold recognition, ab initio prediction, or docking) by testing the consistency between cross-linking data and model geometry. This paper develops a probabilistic framework for analyzing the information content in cross-linking experiments, accounting for anticipated experimental error. This framework supports a mechanism for planning experiments to optimize the information gained. We evaluate potential experiment plans using explicit trade-offs among key properties of practical importance: discriminability, coverage, balance, ambiguity, and cost. We devise a greedy algorithm that considers those properties and, from a large number of combinatorial possibilities, rapidly selects sets of experiments expected to discriminate pairs of models efficiently. In an application to residue-specific chemical cross-linking, we demonstrate the ability of our approach to plan experiments effectively involving combinations of cross-linkers and introduced mutations. We also describe an experiment plan for the bacteriophage , Tfa chaperone protein in which we plan dicysteine mutants for discriminating threading models by disulfide formation. Preliminary results from a subset of the planned experiments are consistent and demonstrate the practicality of planning. Our methods provide the experimenter with a valuable tool (available from the authors) for understanding and optimizing cross-linking experiments. [source] Analyzing unreplicated 2k factorial designs by examining their projections into k -1 factorsQUALITY AND RELIABILITY ENGINEERING INTERNATIONAL, Issue 3 2010P. Angelopoulos Abstract Unreplicated factorial designs are widely used as experimental designs because of the economy they offer in run size. However, they are difficult to analyze because there are no degrees of freedom left to estimate the experimental error. Many methods have been proposed for the analysis of such designs with Lenth's (Technometrics 1989; 31:469,473) and Dong's (Statist. Sinica 1993; 3:209,217) being the most popular. In this paper we take advantage of the projective property of factorial designs and we propose a simple yet effective method for analyzing unreplicated factorial designs. The results are compared through a simulation study with Lenth's and Dong's methods. Copyright © 2009 John Wiley & Sons, Ltd. [source] Impact and Quantification of the Sources of Error in DNA Pooling DesignsANNALS OF HUMAN GENETICS, Issue 1 2009A. Jawaid Summary The analysis of genome wide variation offers the possibility of unravelling the genes involved in the pathogenesis of disease. Genome wide association studies are also particularly useful for identifying and validating targets for therapeutic intervention as well as for detecting markers for drug efficacy and side effects. The cost of such large-scale genetic association studies may be reduced substantially by the analysis of pooled DNA from multiple individuals. However, experimental errors inherent in pooling studies lead to a potential increase in the false positive rate and a loss in power compared to individual genotyping. Here we quantify various sources of experimental error using empirical data from typical pooling experiments and corresponding individual genotyping counts using two statistical methods. We provide analytical formulas for calculating these different errors in the absence of complete information, such as replicate pool formation, and for adjusting for the errors in the statistical analysis. We demonstrate that DNA pooling has the potential of estimating allele frequencies accurately, and adjusting the pooled allele frequency estimates for differential allelic amplification considerably improves accuracy. Estimates of the components of error show that differential allelic amplification is the most important contributor to the error variance in absolute allele frequency estimation, followed by allele frequency measurement and pool formation errors. Our results emphasise the importance of minimising experimental errors and obtaining correct error estimates in genetic association studies. [source] A genetic algorithm for the identification of conformationally invariant regions in protein moleculesACTA CRYSTALLOGRAPHICA SECTION D, Issue 2 2002Thomas R. Schneider Understanding macromolecular function often relies on the comparison of different structural models of a molecule. In such a comparative analysis, the identification of the part of the molecule that is conformationally invariant with respect to a set of conformers is a critical step, as the corresponding subset of atoms constitutes the reference for subsequent analysis for example by least-squares superposition. A method is presented that categorizes atoms in a molecule as either conformationally invariant or flexible by automatic analysis of an ensemble of conformers (e.g. crystal structures from different crystal forms or molecules related by non-crystallographic symmetry). Different levels of coordinate precision, both for different models and for individual atoms, are taken explicitly into account via a modified form of Cruickshank's DPI [Cruickshank (1999), Acta Cryst. D55, 583,601] and are propagated into error-scaled difference distance matrices [Schneider (2000), Acta Cryst. D56, 715,721]. All pairwise error-scaled difference distance matrices are then analysed simultaneously using a genetic algorithm. The algorithm has been tested on several well known examples and has been found to converge rapidly to reasonable results using a standard set of parameters. In addition to the description of the algorithm, a criterion is suggested for testing the identity of two three-dimensional models within experimental error without any explicit superposition. [source] Magnetic field exposure stiffens regenerating plant protoplast cell wallsBIOELECTROMAGNETICS, Issue 2 2006Toshihiko Haneda Abstract Single suspension-cultured plant cells (Catharanthus roseus) and their protoplasts were anchored to a glass plate and exposed to a magnetic field of 302,±,8 mT for several hours. Compression forces required to produce constant cell deformation were measured parallel to the magnetic field by means of a cantilever-type force sensor. Exposure of intact cells to the magnetic field did not result in any changes within experimental error, while exposure of regenerating protoplasts significantly increased the measured forces and stiffened regenerating protoplasts. The diameters of intact cells or regenerating protoplasts were not changed after exposure to the magnetic field. Measured forces for regenerating protoplasts with and without exposure to the magnetic field increased linearly with incubation time, with these forces being divided into components based on the elasticity of synthesized cell walls and cytoplasm. Cell wall synthesis was also measured using a cell wall-specific fluorescent dye, and no changes were noted after exposure to the magnetic field. Analysis suggested that exposure to the magnetic field roughly tripled the Young's modulus of the newly synthesized cell wall without any lag. Bioelectromagnetics 27:98,104, 2006. © 2005 Wiley-Liss, Inc. [source] Recovery of Homogeneous Polyoxometallate Catalysts from Aqueous and Organic Media by a Mesoporous Ceramic Membrane without Loss of Catalytic ActivityCHEMISTRY - A EUROPEAN JOURNAL, Issue 11 2006Sankhanilay Roy Chowdhury Dr. Abstract The recovery of homogeneous polyoxometallate (POM) oxidation catalysts from aqueous and non-aqueous media by a nanofiltration process using mesoporous ,-alumina membranes is reported. The recovery of Q12[WZn3(ZnW9O34)2] (Q=[MeN(n -C8H17)3]+) from toluene-based media was quantitative within experimental error, while up to 97,% of Na12[WZn3(ZnW9O34)2] could be recovered from water. The toluene-soluble POM catalyst was used repeatedly in the conversion of cyclooctene to cyclooctene oxide and separated from the product mixture after each reaction. The catalytic activity increased steadily with the number of times that the catalyst had been recycled, which was attributed to partial removal of the excess QCl that is known to have a negative influence on the catalytic activity. Differences in the permeability of the membrane for different liquid media can be attributed to viscosity differences and/or capillary condensation effects. The influence of membrane pore radius on permeability and recovery is discussed. [source] | |||||||||||||||||||||||||||||||||||||