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A new approach to analyze multi-component Saturation Transfer Difference (STD) NMR spectra by combining the STD and the DOSY experiment is proposed. The resulting pulse sequence was successfully used to simplify an exemplary multi- component protein/substrate system by means of standard DOSY processing methods. Furthermore, the same experiment could be applied to calculate the ratio of saturated substrate molecules and its saturation rate in the case of competitive interactions. This ratio depends on the strength of this interaction between the substrates and the protein, so that this kind of information could be extracted from the results of our experiment.
The through space NMR shieldings (TSNMRS) of dodecahedrane C20H20, of the isomeric hydrocarbons C20H12, of the ions C20H122+ and C20H122- of the fluxional fullerene C20 and of its dication C202+ have been ab initio calculated employing the NICS concept on basis of MP2/6-31G* geometries and visualized as iso-chemical-shielding/deshielding surfaces (ICSSs). TSNMRS values were employed to study the exohedral magnetic properties of the compounds studied. Hereby, the curved It-conjugation in the compounds studied could be quantified.
The clerodane diterpenoids trans-kolavenolic acid, 18-oxocleroda-3,13(E)-dien-15-oic acid, ent-(18- hydroxycarbonyl)-cleroda- 3,13(E)-dien-15-oate, 2-oxo-ent-cleroda-3,13(Z)-dien-15-oic acid and trans-2-oxo-ent-cleroda- 13(Z)-en-15-oic acid, and the chlorobenzenoid O-(3-hydroxy-4-hydroxycarbonyl-5-pentylphenyl)-3-chloro-4-methoxy-6-pentyl- 2-oxybenzoic acid were isolated from Tessmannia martiniana var pauloi and T. martiniana var matiniana. Structures were established based on interpretation of spectroscopic data. Some of the compounds exhibited significant antimosquito, antifungal and antibacterial activities.
Influence of land-use change on near-surface hydrological processes : undisturbed forest to pasture
(2010)
Soil compaction that follows the clearing of tropical forest for cattle pasture is associated with lower soil hydraulic conductivity and increased frequency and volume of overland flow. We investigated the frequency of perched water tables, overland flow and stormflow in an Amazon forest and in an adjacent 25-year-old pasture cleared from the same forest. We compared the results with the frequencies of these phenomena estimated from comparisons of rainfall intensity and soil hydraulic conductivity. The frequency of perched water tables based on rainfall intensity and soil hydraulic conductivity was expected to double in pasture compared with forest. This corresponded closely with an approximate doubling of the frequency of stormflow and overland flow in pasture. In contrast, the stormflow volume in pasture increased 17-fold. This disproportional increase of stormflow resulted from overland flow generation over large areas of pasture, while overland flow generation in the forest was spatially limited and was observed only very near the stream channel. In both catchments, stormflow was generated by saturation excess because of perched water tables and near-surface groundwater levels. Stormflow was occasionally generated in the forest by rapid return flow from macropores, while slow return flow from a continuous perched water table was more common in the pasture. These results suggest that deforestation for pasture alters fundamental mechanisms of stormflow generation and may increase runoff volumes over wide regions of Amazonia.
The hydrologic cycle of high mountainous catchments is frequently simulated with simple precipitation-discharge models representing the snow accumulation and ablation behavior of a very complex environment with a set of lumped equations accounting for altitudinal temperature and precipitation gradients. In this study, we present a methodology to include sparse snow depths measurements into the calibration process. Based on this methodology, we assess for a case study, the Rhonegletscher catchment (Switzerland), how much observed information we need to reliably calibrate the model, such that it reproduces the dominant system dynamics, discharge, as well as glacier mass balance. Here, we focus on the question whether observed discharge is sufficient as a calibration variable or whether we need annual or even seasonal glacier mass balance data. Introducing seasonally variable accumulation and ablation parameters is sufficient to enable the simple model to reproduce observed seasonal mass balances for the Rhonegletscher. Furthermore, our results suggest that calibrating the hydrological model exclusively on discharge can lead to wrong representations of the intra- annual accumulation and ablation processes and to a strong bias in long term glacier mass balance simulations. Adding only a few annual mass balance observations considerably reduces this bias. Calibrating exclusively on annual balance data can, in turn, lead to wrong seasonal mass balance simulations. Even if these results are case study specific, our conclusions provide valuable new insights into the benefit of different types of observations for calibrating hydrological models in glacier catchments. The presented multi-signal calibration framework and the simple method to calibrate a semi-lumped model on point observations has potential for application in other modeling contexts.
Investigation of transient soil moisture profiles yields valuable information of near- surface processes. A recently developed reconstruction algorithm based on the telegraph equation allows the inverse estimation of soil moisture profiles along coated, three rod TDR probes. Laboratory experiments were carried out to prove the results of the inversion and to understand the influence of probe rod deformation and solid objects close to the probe in heterogonous media. Differences in rod geometry can lead to serious misinterpretations in the soil moisture profile but have small influence on the average soil moisture along the probe. Solids in the integration volume have almost no effect on average soil moisture but result in locally slightly decreased moisture values. Inverted profiles obtained in a loamy soil with a clay content of about 16% were in good agreement with independent measurements.
Applying metrics for hydrograph comparison is a central task in hydrological modelling, used both in model calibration and the evaluation of simulations or forecasts. Motivated by the shortcomings of standard objective metrics such as the Root Mean Square Error or the Mean Peak Time Error and the advantages of visual inspection as a powerful tool for simultaneous, case-specific and multi-criteria (yet subjective) evaluation, we propose a new objective metric termed Series Distance, which is in close accordance with visual evaluation. The Series Distance is an event-based method and consists of three parts, namely a Threat Score which evaluates overall agreement of event occurrence, and the overall distance of matching observed and simulated events with respect to amplitude and timing. The novelty of the latter two is the way in which matching point pairs on the observed and simulated hydrographs are identified, namely by the same relative position in matching segments (rise or recession) of matching events. Thus, amplitude and timing errors are calculated simultaneously but separately, from point pairs that also match visually, considering complete events rather than only individual points (which is for example the case with metrics related to Peak Time Errors). After presenting the Series Distance theory, we discuss its properties and compare it to those of standard metrics and visual inspection, both at the example of simple, artificial hydrographs and an ensemble of realistic forecasts. The results suggest that the Series Distance compares and evaluates hydrographs in a way comparable to visual inspection, but in an objective, reproducible way.
During the last glacial period, climate records from the North Atlantic region exhibit a pronounced spectral component corresponding to a period of about 1470 years, which has attracted much attention. This spectral peak is closely related to the recurrence pattern of Dansgaard-Oeschger (DO) events. In previous studies a red noise random process, more precisely a first-order autoregressive (AR1) process, was used to evaluate the statistical significance of this peak, with a reported significance of more than 99%. Here we use a simple mechanistic two-state model of DO events, which itself was derived from a much more sophisticated ocean-atmosphere model of intermediate complexity, to numerically evaluate the spectral properties of random (i.e., solely noise-driven) events. This way we find that the power spectral density of random DO events differs fundamentally from a simple red noise random process. These results question the applicability of linear spectral analysis for estimating the statistical significance of highly non-linear processes such as DO events. More precisely, to enhance our scientific understanding about the trigger of DO events, we must not consider simple "straw men" as, for example, the AR1 random process, but rather test against realistic alternative descriptions.
In one of the data mining techniques, change-point detection is of importance in evaluating time series measured in real world. For decades this technique has been developed as a nonlinear dynamics. We apply the method for detecting the change points, Singular Spectrum Transformation (SST), to the climate time series. To know where the structures of climate data sets change can reveal a climate background. In this paper we discuss the structures of precipitation data in Kenya and Wrangel Island (Arctic land) by using the SST.
Narrow channels with polar walls are the structural and functional features responsible for the high capacity of a zinc-organic framework based on an imidazolate-amide-imidate ligand for the uptake of H2 and CO2 (see structure: orange Zn, blue N, red O, dark gray C, light gray H). The rigid and stable chelating ligand was synthesized in situ by partial hydrolysis of a dicyanoimidazole compound.
Cork is a natural cellular and electrically insulating material which may have the capacity to store electric charges on or in its cell walls. Since natural cork has many voids, it is difficult to obtain uniform samples with the required dimensions. Therefore, a more uniform material, namely commercial cork agglomerate, usually used for floor and wall coverings, is employed in the present study. Since we know from our previous work that the electrical properties of cork are drastically affected by absorbed and adsorbed water, samples were protected by means of different polymer coatings (applied by spin-coating or soaking). Corona charging and isothermal charging and discharging currents were used to study the electrical trapping and detrapping capabilities of the samples. A comparison of the results leads to the conclusion that the most promising method for storing electric charges in this cellular material consists of drying and coating or soaking with a hydrophobic, electrically insulating polymer such as polytetraflouroethylene (Teflon (R)). (c) 2007 Elsevier B.V. All rights reserved.
Using the gaze-contingent boundary paradigm with the boundary placed after word n, the experiment manipulated preview of word n + 2 for fixations on word n. There was no preview benefit for 1st-pass reading on word n + 2, replicating the results of K. Rayner, B. J. Juhasz, and S. J. Brown (2007), but there was a preview benefit on the 3- letter word n + 1, that is, after the boundary but before word n + 2. Additionally, both word n + 1 and word n + 2 exhibited parafoveal-on-foveal effects on word n. Thus, during a fixation on word n and given a short word n + 1, some information is extracted from word n + 2, supporting the hypothesis of distributed processing in the perceptual span.
Mono- and trans-1,4-dialkoxy substituted cyclohexanes (alkyl=Me, Et, i-Pr, t-Bu) were prepared using the solvomercuration-demercuration (SM-DM) procedure. The axialaxial and axial,axialequatorial, equatorial conformational equilibria of the products were studied by low temperature 1H and 13C NMR spectroscopy in CD2Cl2. The structures and relative energies of the participating conformers were calculated at both the B3LYP (6-311G*//6-311+G*) and MP2 (6-311+G*//6-311G*) levels of theory. In the case of DFT, good correlations of ;Gocalcd versus ;Goexptl were obtained. Both the structures and the energy differences of the conformers have been discussed with respect to established models of conformational analysis, viz. steric and hyperconjugative interactions. In addition, 1JH,C coupling constants were considered with respect to the hyperconjugation present.
Through space NMR shieldings of aromatic (benzene, mono-substituted and annelated benzenes, ferrocene, [14]- and [18]-annulenes, phenylenes and tetra- to heptahelicene) and anti-aromatic molecules (cyclobutadiene and pentalene) were assessed by ab initio molecular-orbital calculations. Employing the nucleus-independent chemical shifts (NICS) concept, these through space NMR shieldings were visualized as iso-chemical-shielding surfaces (ICSSs) and can be applied quantitatively to determine the stereochemistry of proximal nuclei. In addition, the distances in Å at ICSS values of ±0.1 ppm in-plane and perpendicular-to-center of the aromatic ring system were employed as a simple means to compare and estimate qualitatively the aromaticity of the systems at hand.
The influence of Daphnia galeata x hyalina grazing and of infochemicals released by the daphnids on the colony size and growth rate of the colonial gelatinous green alga Sphaerocystis schroeteri (Chlorococcales) was investigated in laboratory batch experiments run for 96 h. High zooplankton grazing pressure was exerted by a final concentration of 100 daphnids L-1 in the Daphnia treatments. Infochemicals were obtained by filtration (0.2 µm) of water from D. galeata x hyalina cultures (200 ind. L-1 exposed for 24 h). This filtrate was added to the S. schroeteri cultures in two concentrations corresponding to 7 and 50 daphnids L-1, respectively. The growth rate of S. schroeteri was neither affected significantly by direct Daphnia grazing nor by the presence of Daphnia infochemicals in comparison to the control. However, the portion of inedible S. schroeteri colonies (diameter > 50 µm) increased under direct grazing pressure, whereas the Daphnia infochemicals did not influence the colony size significantly. We conclude that the shift in colony size by direct zooplankton grazing denotes an effective defence mechanism against size selective feeding for colonial gelatinous green algae. This effective defence in combination with unchanged growth rates of the larger colonies (under non-limiting nutrient and light conditions) falsifies the assumption of a trade-off between minimising grazing losses and maximising growth by optimising the colony size.
In population ecology, there has been a fundamental controversy about the relative importance of competition- driven (density-dependent) population regulation vs. abiotic influences such as temperature and precipitation. The same issue arises at the community level; are population sizes driven primarily by changes in the abundances of cooccurring competitors (i.e., compensatory dynamics), or do most species have a common response to environmental factors? Competitive interactions have had a central place in ecological theory, dating back to Gleason, Volterra, Hutchison and MacArthur, and, more recently, Hubbell's influential unified neutral theory of biodiversity and biogeography. If competitive interactions are important in driving year-to-year fluctuations in abundance, then changes in the abundance of one species should generally be accompanied by compensatory changes in the abundances of others. Thus, one necessary consequence of strong compensatory forces is that, on average, species within communities will covary negatively. Here we use measures of community covariance to assess the prevalence of negative covariance in 41 natural communities comprising different taxa at a range of spatial scales. We found that species in natural communities tended to covary positively rather than negatively, the opposite of what would be expected if compensatory dynamics were important. These findings suggest that abiotic factors such as temperature and precipitation are more important than competitive interactions in driving year-to-year fluctuations in species abundance within communities.
A novel electrochemical immunoassay based on the multiple affinity labeling of the indicator antibody with an electro-active tag is presented. The concept is illustrated for the determination of the glycated hemoglobin HbA1c in hemoglobin samples. Hemoglobin is adsorbed to the surfactant-modified surface of a piezoelectric quartz crystal. Whereas the quartz crystal nanobalance is used to validate the total Hb binding, the HbA1c on the sensor surface is recognized by an antibody and quantified electrochemically after the sugar moieties of the antibody have been labeled in-situ with ferroceneboronic acid. The sensitivity of this sensor is about threefold higher than the sensitivity of a hemoglobin sensor, where the ferroceneboronic acid is bound directly to HbA1c.
The development of an electrochemical piezoelectric sensor for the detection of glycated hemoglobin is presented. The total hemoglobin (Hb) content is monitored with a mass-sensitive quartz crystal modified with surfactants, and the glycated fraction of the immobilized Hb is determined by subsequent voltarnmetric measurement of the coupled ferroceneboronic acid. Different modifications of the sensor were tested for their hemoglobin binding ability. Deoxycholate (DOCA) was found to be the most suitable among the examined modifiers. Piezoelectric quartz crystals with gold electrodes were modified with DOCA by covalent binding to a pre-formatted 4-aminothiophenol monolayer. The properties of the Hb binding to DOCA and the pH effect on this interaction were studied. In the proposed assay for glycated hemoglobin at first an Hb sample is incubated with ferroceneboronic acid (FcBA), which binds to the fructosyl residue of the glycated Hb. Then this preincubated Hb sample is allowed to interact with the DOCA-modified piezoelectric quartz crystal. The binding is monitored by quartz crystal nanobalance QCN). The amount of FcBA present on the sensor surface is determined by square wave voltammetry. The binding of FcBA results in well-defined peaks with an EO' of +200 mV versus Ag/AgC1 (1 M KC1). The peak height depends on the degree of glycated Hb in the sample ranging from 0% to 20% of total Hb. The regeneration of the sensing surface is achieved by pepsin digestion of the deposited Hb. Thus the sensor can be re-used more than 30 times.
Heterochitooligosaccharides possess interesting biol. properties. Isobaric mixts. of such linear heterochitooligosaccharides can be obtained by chem. or enzymic degrdn. of chitosan. However, the sepn. of such mixts. is a challenging anal. problem which is so far unresolved. It is shown that these isobaric mixts. can be sequenced and quantified simultaneously using std. derivatization and multistage tandem mass spectrometric techniques. A linear ion trap mass spectrometer equipped with a vacuum matrix-assisted laser desorption ionization (vMALDI) source is used to perform MS2 as well as MS3 expts. [on SciFinder (R)].
This contribution presents an approach for requirement oriented team building in industrial processes like product development. This will be based on the knowledge modelling and description language (KMDL(R)) that enables the modelling and analysis of knowledge intensive business processes. First the basic elements of the modelling technique are described, presenting the concept and the description language. Furthermore it is shown how the KMDL(R) process models can be used as a basis for the team building component. Therefore, an algorithm was developed that is able to propose a team composition for a specific task by analyzing the knowledge and skills of the employees, which will be contrasted to the process requirements. This can be used as guidance for team building decisions.