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The aim of the present study was to investigate the test-retest reliability of the olfactory detection threshold subtest of the Sniffin" Sticks test battery, if administered repeatedly on 4 time points. The detection threshold test was repeatedly conducted in 64 healthy subjects. On the first testing session, the threshold test was accomplished 3 times (T(1) = 0 min, T(2) = 35 min, and T(3) = 105 min), representing a short-term testing. A fourth threshold test was conducted on a second testing session (T(4) = 35.1 days after the first testing session), representing a long-term testing. The average scores for olfactory detection threshold for n-butanol did not differ significantly across the 4 points of time. The test-retest reliability (Pearson"s r) between the 4 time points of threshold testing were in a range of 0.43-0.85 (P < 0.01). These results support the notion that the olfactory detection threshold test is a highly reliable method for repeated olfactory testing, even if the test is repeated more than once per day and over a long-term period. It is concluded that the olfactory detection threshold test of the Sniffin" Sticks is suitable for repeated testing during experimental or clinical studies.
Oidium pedaliacearum sp. nov. (; O. sesami, nom. inval.) and Podosphaera macrospora comb. et stat. nov. (; Sphaerotheca alpina f. macrospora) are introduced, and the taxonomy and distribution of Erysiphe celosiae is discussed. New host species and new collections of Erysiphe cruciferarum (on Cleome hassleriana), E. flexuosa (on Aesculus hippocastanum), E. hedwigii (on Viburnum carlesii), E. heraclei (on Tinguarra montana), E. cf. macleayae (on Macleaya cordata), E. prunastri (on Prunus cerasifera), E. sedi (on Sedum aff. spectabilis), E. trifolii (on Trigonella caerulea), Golovinomyces cichoracearum (on Argyranthemum pinnatifidum subsp. succulentum), G. cf. hydrophyllacearum (on Nemophila menziesii), G. orontii (on Nolana spp.), G. cf. orontii (on Tiarella cordifolia), Neoerysiphe cumminsiana (on Bidens cf. ferulifolia), Oidium clitoriae (on Clitoria ternatea), O. cf. hortensiae (on Philadelphus coronarius), O. pedilanthi (on Pedilanthus tithymaloides), Oidium (Pseudoidium) sp. (on Utricularia alpina), Podosphaera sp. (on Bergia capensis), Sawadaea bicornis (on Acer platanoides) and S. tulasnei (on Acer ginnala and A. tatarica) are recorded from France, Germany, Greece and Mexico.
The boundary paradigm (Rayner, 1975) with a novel preview manipulation was used to examine the extent of parafoveal processing of words to the right of fixation. Words n + 1 and n + 2 had either correct or incorrect previews prior to fixation (prior to crossing the boundary location). In addition, the manipulation utilized either a high or low frequency word in word n + 1 location on the assumption that it would be more likely that n + 2 preview effects could be obtained when word n + 1 was high frequency. The primary findings were that there was no evidence for a preview benefit for word n + 2 and no evidence for parafoveal-on-foveal effects when word n + 1 is at least four letters long. We discuss implications for models of eye-movement control in reading.
Choice-based Conjointanalyse
(2008)
A new series of unsubstituted and substituted pyridinium salts bearing a 4-oxothiazolidinyl moiety has been prepared by an efficient rearrangement of 2-(1-bromoalkylidene)thiazolidin-4-ones. The process in based on three steps, namely carbon-bromine cleavage, bromine transfer, and substitution, each induced by pyridine or its derivatives, acting as base and reactant.
Bacteriophage HK620 infects Escherichia coli H and is closely related to Shigella phage Sf6 and Salmonella phage P22. All three Podoviridae recognize and cleave their respective host cell receptor polysaccharide by homotrimeric tailspike proteins. The three proteins exhibit high sequence identity in the 110 residues of their N-terminal particle- binding domains, but no apparent sequence similarity in their major, receptor-binding parts. We have biochemically characterized the receptor-binding part of HK620 tailspike and determined its crystal structure to 1.38 Å resolution. Its major domain is a right-handed parallel ;-helix, as in Sf6 and P22 tailspikes. HK620 tailspike has endo-N- acetylglucosaminidase activity and produces hexasaccharides of an O18A1-type O-antigen. As indicated by the structure of a hexasaccharide complex determined at 1.6 Å resolution, the endoglycosidase-active sites are located intramolecularly, as in P22, and not between subunits, as in Sf6 tailspike. In contrast, the extreme C-terminal domain of HK620 tailspike forms a ;-sandwich, as in Sf6 and unlike P22 tailspike. Despite the different folds, structure-based sequence alignments of the C-termini reveal motifs conserved between the three proteins. We propose that the tailspike genes of P22, Sf6 and HK620 have a common precursor and are not mosaics of unrelated gene fragments.
Soils play a crucial role in biogeochemical cycles as spatially distributed sources and sinks of nutrients. Any spatial patterns depend on soil forming processes, our understanding of which is still limited, especially in regards to tropical rainforests. The objective of our study was to investigate the effects of landscape properties, with an emphasis on the geometry of the land surface, on the spatial heterogeneity of soil chemical properties, and to test the suitability of soil-landscape modeling as an appropriate technique to predict the spatial variability of exchangeable K and Mg in a humid tropical forest in Panama. We used a design-based, stratified sampling scheme to collect soil samples at 108 sites on Barro Colorado Island, Panama. Stratifying variables are lithology, vegetation and topography. Topographic variables were generated from high-resolution digital elevation models with a grid size of 5 m. We took samples from five depths down to I m, and analyzed for total and exchangeable K and Mg. We used simple explorative data analysis techniques to elucidate the importance of lithology for soil total and exchangeable K and Mg. Classification and Regression Trees (CART) were adopted to investigate importance of topography, lithology and vegetation for the spatial distribution of exchangeable K and Mg and with the intention to develop models that regionalize the point observations using digital terrain data as explanatory variables. Our results suggest that topography and vegetation do not control the spatial distribution of the selected soil chemical properties at a landscape scale and lithology is important to some degree. Exchangeable K is distributed equally across the study area indicating that other than landscape processes, e.g. biogeochemical processes, are responsible for its spatial distribution. Lithology contributes to the spatial variation of exchangeable Mg but controlling variables could not be detected. The spatial variation of soil total K and Mg is mainly influenced by lithology.
Objective To demonstrate that children homozygous for the 10-repeat allele of the common dopamine transporter (DAT1) polymorphism who were exposed to maternal prenatal smoke exhibited significantly higher hyperactivity-impulsivity than children without these environmental or genetic risks. Study design We performed a prospective longitudinal study from birth into early adulthood monitoring the long-term outcome of early risk factors. Maternal prenatal smoking was determined during a standardized interview with the mother when the child was 3 months old. At age 15 years, 305 adolescents participated in genotyping for the DAT1 40 base pair variable number of tandem repeats polymorphism and assessment of inattention, hyperactivity-impulsivity, and oppositional defiant/conduct disorder symptoms with die Kiddie- Sads-Present and Lifetime Version. Results There was no bivariate association between DAT1 genotype, prenatal smoke exposure and symptoms of attention deficit hyperactivity disorder. However, a significant interaction between DAT1 genotype and prenatal smoke exposure emerged (P =.012), indicating that males with prenatal smoke exposure who were homozygous for the DAT1 10r allele had higher hyperactivity-impulsivity than males from all other groups. In females, no significant main effects of DAT1 genotype or prenatal smoke exposure or interaction effects on any symptoms were evident (all P >.25). Conclusions This study provides further evidence for the multifactorial nature of attention deficit hyperactivity disorder and the importance of studying both genetic and environmental factors and their interaction.
* 1. Large female insects usually have high potential fecundity. Therefore selection should favour an increase in body size given that these females get opportunities to realize their potential advantage by maturing and laying more eggs. However, ectotherm physiology is strongly temperature-dependent, and activities are carried out sufficiently only within certain temperature ranges. Thus it remains unclear if the fecundity advantage of a large size is fully realized in natural environments, where thermal conditions are limiting. * 2. Insect fecundity might be limited by temperature at two levels; first eggs need to mature, and then the female needs time for strategic ovipositing of the egg. Since a female cannot foresee the number of oviposition opportunities that she will encounter on a given day, the optimal rate of egg maturation will be governed by trade-offs associated with egg- and time-limited oviposition. As females of different sizes will have different amounts of body reserves, size-dependent allocation trade-offs between the mother"s condition and her egg production might be expected. * 3. In the temperate butterfly Pararge aegeria, the time and temperature dependence of oviposition and egg maturation, and the interrelatedness of these two processes were investigated in a series of laboratory experiments, allowing a decoupling of the time budgets for the respective processes. * 4. The results show that realized fecundity of this species can be limited by both the temperature dependence of egg maturation and oviposition under certain thermal regimes. Furthermore, rates of oviposition and egg maturation seemed to have regulatory effects upon each other. Early reproductive output was correlated with short life span, indicating a cost of reproduction. Finally, large females matured more eggs than small females when deprived of oviposition opportunities. Thus, the optimal allocation of resources to egg production seems dependent on female size. * 5. This study highlights the complexity of processes underlying rates of egg maturation and oviposition in ectotherms under natural conditions. We further discuss the importance of temperature variation for egg- vs. time-limited fecundity and the consequences for the evolution of female body size in insects.
Competition is a key process in plant populations and communities. We thus need, if we are to predict the responses of ecological systems to environmental change, a comprehensive and mechanistic understanding of plant competition. Considering competition, however, only at the population level is not sufficient because plant individuals usually are different, interact locally, and can adapt their behaviour to the current state of themselves and of their biotic and abiotic environment. Therefore, simulation models that are individual-based and spatially explicit are increasingly used for studying competition in plant systems. Many different individual-based modelling approaches exist to represent competition, but it is not clear how good they are in reflecting essential aspects of plant competition. We therefore first summarize current concepts and theories addressing plant competition. Then, we review individual-based approaches for modelling competition among plants. We distinguish between approaches that are used for more than 10 years and more recent ones. We identify three major gaps that need to be addressed more in the future: the effects of plants on their local environment, adaptive behaviour, and below-ground competition. To fill these gaps, the representation of plants and their interactions have to be more mechanistic than most existing approaches. Developing such new approaches is a challenge because they are likely to be more complex and to require more detailed knowledge and data on individual-level processes underlying competition. We thus need a more integrated research strategy for the future, where empirical and theoretical ecologists as well as computer scientists work together on formulating, implementing, parameterization, testing, comparing, and selecting the new approaches. (c) 2008 Rubel Foundation, ETH Zurich. Published by Elsevier GmbH. All rights reserved.
A chemotaxonomic evaluation using hplc profiling was undertaken to resolve the infrageneric and intergeneric affinities of over 150 strains of Xylariaceae. Daldinia placentiformis, Hypoxylon nicaraguense, H. polyporus, and Phylacia sagrana were found to contain 8-methoxy-1-naphthol, which is apparently absent in Annulohypoxylon, Hypoxylon, and related genera with bipartite stromata. D. placentiformis and other species of Daldinia and Entonaema produced this naphthol, 5-hydroxy-2-methylchromone, isosclerone derivatives, and 'AB-5046' phytotoxins. Phylacia sagrana differed from most Daldinia spp., except for D. caldariorum, by producing eutypine derivatives in addition to the above compounds. indolylquinones were observed in H. nicaraguense and H. polyporus. Isosclerones were also identified in the A. multiforme complex, but Hypoxylon and other Annulohypoxylon and most Hypoxylon spp. studied Annulohypoxylon spp. contained S-methylmellein as the major metabolite of their cultures. Based on the occurrence of the above metabolites, further mellein-type dihydroisocoumarins, teleomorphic and anamorphic Xylariaceae with Nodulisporium-like anamorphs ('Hypoxyloideae') were divided into various chemotypes. A comparison of their 5.8S/ ITS nuc-rDNA sequences agreed in some important aspects with the above results: H. nicaraguense and H. polyporus appeared basal to a clade comprising Daldinia, Entonaema, and Ph. sagrana. The latter species appeared allied to D. caldariorum, but was distantly related to Pyrenomyxa morganii and Hypoxylon s. str. (C) 2007 The British Mycological Society. Published by Elsevier Ltd. All rights reserved.
Seasonal differences in spatial distribution of small carnivores in fragmented savannah landscapes
(2008)
Monitoring animal populations in changing environments is crucial to wildlife conservation and management, but restrictions in resources are a recurring problem for wildlife managers and researchers throughout Africa. Land-use- induced shrub encroachment in Kalahari savannah rangelands has led to fragmentation of the landscape. Mammalian carnivores are particularly vulnerable to local extinction in fragmented landscapes, but their low numbers and their often nocturnal and secretive habits make them difficult to monitor. In this study, we tested the applicability of a passive tracking method and compared two measurement methods and index calculations for monitoring small carnivores across a grazing gradient in the southern Kalahari. During the four years of monitoring in a five-year period, we used the knowledge of indigenous Khoisan Bushmen for the identification of carnivore tracks on 640 sand transects (5 m x 250 m). Our results showed that this simple and inexpensive observation method enabled detailed monitoring of 10 small carnivore species across the grazing gradient. A binary index calculated an index based on presence/absence of a species' tracks on each transect, whereas the track intrusion index used the number of track intrusions to each transect for each species in its calculations. For less common species, the two indices were similar in trend and magnitude, because the number of intrusions to each transect was typically 1 or 0. Usually, the two indices showed relatively strong correlations. However, species with patchy distributions of higher numbers presented difficulties for the binary index to monitor trends, but not for the track intrusion index.
Parsing costs as predictors of reading difficulty : an evaluation using the Potsdam Sentence Corpus
(2008)
The introduction of a new powdery mildew disease on Rhus hirta in various parts of Germany (Brandenburg, Rhine- Westphalia, Sachsen-Anhalt and Saxony) is reported. The anamorph found on this host agrees well with the North American Podosphaera pruinosa. Although the teleomorph has not yet been found in Germany and a molecular study has not yet been possible due to the lack of fresh North American material for a comparison, there is little doubt that the European outbreak of the Rhus powdery mildew disease may be referred to as Podosphaera pruinosa. Morphology, taxonomy and distribution of Podosphaera species on Rhus and other hosts of the Anacardiaceae are discussed in detail.
From the roots of the African plant Bulbine frutescens (Asphodelaceae), two unprecedented novel dimeric phenylanthraquinones, named joziknipholones A and B, possessing axial and centrochirality, were isolated, together with six known compounds. Structural elucidation of the new metabolites was achieved by spectroscopic and chiroptical methods, by reductive cleavage of the central bond between the monomeric phenylanthraquinone and -anthrone portions with sodium dithionite, and by quantum chemical CD calculations. Based on the recently revised absolute axial configuration of the parent phenylanthraquinones, knipholone and knipholone anthrone, the new dimers were attributed to possess the P- configuration (i.e., with the acetyl portions below the anthraquinone plane) at both axes in the case of joziknipholone A, whereas in joziknipholone B, the knipholone part was found to be M-configured. Joziknipholones A and B are active against the chloroquine resistant strain K1 of the malaria pathogen, Plasmodium falciparum, and show moderate activity against murine leukemic lymphoma L5178y cells.
Traffic of molecular motors
(2008)
In this microreview we describe the principle of Forster resonance energy transfer (FRET) occurring between closely spaced energy-donor and -acceptor molecules. The theoretical treatment is depicted in relation with the data extractable from spectroscopic measurements. We present the specific case of semiconductor nanocrystals (or quantum dots QDs) as energy donors in FRET experiments and a particular emphasis is put on the specific advantages of these fluorophores with regard to both their exceptional photophysical properties and their nanoscopic morphology. In a following section, the special attributes of luminescent lanthanide complexes (LLCs) are outlined with illustrations of properties such as their characteristic emission spectra, long-lived luminescence, and large "Stokes shift". Finally, the successful combination of LLCs and QDs in FRET experiments is demonstrated, showing the unrivaled benefits of this singular marriage, opening doors for energy transfer at very large distances and excellent sensitivity of detection within the frame of time-resolved fluoroimmunoassays. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
We consider diffusion processes with a spatially varying diffusivity giving rise to anomalous diffusion. Such heterogeneous diffusion processes are analysed for the cases of exponential, power-law, and logarithmic dependencies of the diffusion coefficient on the particle position. Combining analytical approaches with stochastic simulations, we show that the functional form of the space-dependent diffusion coefficient and the initial conditions of the diffusing particles are vital for their statistical and ergodic properties. In all three cases a weak ergodicity breaking between the time and ensemble averaged mean squared displacements is observed. We also demonstrate a population splitting of the time averaged traces into fast and slow diffusers for the case of exponential variation of the diffusivity as well as a particle trapping in the case of the logarithmic diffusivity. Our analysis is complemented by the quantitative study of the space coverage, the diffusive spreading of the probability density, as well as the survival probability.
We present a general framework for integrating annotations from different tools and tag sets. When annotating corpora at multiple linguistic levels, annotators may use different expert tools for different phenomena or types of annotation. These tools employ different data models and accompanying approaches to visualization, and they produce different output formats. For the purposes of uniformly processing these outputs, we developed a pivot format called PAULA, along with converters to and from tool formats. Different annotations are not only integrated at the level of data format, but are also joined on the level of conceptual representation. For this purpose, we introduce OLiA, an ontology of linguistic annotations that mediates between alternative tag sets that cover the same class of linguistic phenomena. All components are integrated in the linguistic information system ANNIS : Annotation tool output is converted to the pivot format PAULA and read into a database where the data can be visualized, queried, and evaluated across multiple layers. For cross-tag set querying and statistical evaluation, ANNIS uses the ontology of linguistic annotations. Finally, ANNIS is also tied to a machine learning component for semiautomatic annotation.
Increasing production activities have been observed in many EU member states since the EU Commission sent a clear signal establishing and supporting the bioenergy industry. This article discusses current sector developments and therewith evolving biofuel value chain activities and management requirements by means of two German biofuel processing firms. Usually, the processing company can be regarded as the initiator of the regional value chains. In order to safeguard the high initial investments and secure efficient supply, the processing company relies on contract farming or profit participation rights rather than spot market interactions. In addition to discussing that point, this paper also explores opportunities and threats for the suppliers of raw materials as well as for the processors.
Efficient triplet exciton emission has allowed improved operation of organic light-emitting diodes (LEDs). To enhance the device performance, it is necessary to understand what governs the motion of triplet excitons through the organic semiconductor. Here, we have investigated triplet diffusion using a model compound that has weak energetic disorder. The Dexter-type triplet energy transfer is found to be thermally activated down to a transition temperature T- T, below which the transfer rate is only weakly temperature dependent. We show that above the transition temperature, Dexter energy transfer can be described within the framework of Marcus theory. We suggest that below T-T, the nature of the transfer changes from phonon-assisted hopping to quantum-mechanical tunneling. The lower electron-phonon coupling and higher electronic coupling in the polymer compared to the monomer results in an enhanced triplet diffusion rate.
Many Christians react in alarm when being confronted with reincarnation. They tend to regard it as an alien or exotic idea or sometimes even as an occult or dangerous teaching that leads away from the Christian path. Thus, belief in rebirth is often regarded as clearly not compatible with orthodox Christianity. However, no less than 30% of people in the Western world believe in a form of reincarnation, which indicates the urgency for an academic examination of this subject. Patrick Diemling examines under what conditions or restrictions a person who is attracted by the notion of reincarnation could at the same time remain fundamentally loyal to Christ. In a survey through the pivotal sections of Christian theology (such as soteriology, cosmology and eschatology), he investigates the critical points regarding the question of a possible compatibility of reincarnation with the Christian faith. What does the Bible say about reincarnation? What are the points of disagreement between orthodox Christians and defenders of the idea of rebirth? How would Christian theology need to be modified so as to integrate belief in reincarnation? The present volume tries to answer these questions.
Fred D'Aguiar
(2008)
Dionne Brand
(2008)
Caryl Phillips
(2008)
Modelling and empirical studies have shown that input from the regional seed pool is essential to maintain local species diversity. However, most of these studies have concentrated on simplified, if not neutral, model systems, and focus on a limited subset of species or on aggregated measures of diversity only (e.g., species richness or Shannon diversity). Thus they ignore more complex species interactions and important differences between species. To gain a better understanding of how seed immigration affects community structure at the local scale in real communities we conducted computer simulation experiments based on plant functional types (PFTs) for a species-rich, fire-prone Mediterranean-type shrubland in Western Australia. We developed a spatially explicit simulation model to explore the community dynamics of 38 PFTs, defined by seven traits - regeneration mode, seed production, seed size, maximum crown diameter, drought tolerance, dispersal mode and seed bank type - representing 78 woody species. Model parameterisation is based on published and unpublished data on the population dynamics of shrub species collected over 18 years. Simulation experiments are based on two contrasting seed immigration scenarios: (1) the 'equal seed input number' scenario, where the number of immigrant seeds is the same for all PFTs, and (2) the 'equal seed input mass' scenario, where the cumulative mass of migrating seeds is the same for all PFTs. Both scenarios were systematically tested and compared for different overall seed input values. Without immigration the local community drifts towards a state with only 13 coexisting PFTs. With increasing immigration rates in terms of overall mass of seeds the simulated number of coexisting PFTs and Shannon diversity quickly approaches values observed in the field. The equal seed mass scenario resulted in a more diverse community than did the seed number scenario. The model successfully approximates the frequency distributions (relative densities) of all individual plant traits except seed size for scenarios associated with equal seed input mass and high immigration rate. However, no scenario satisfactorily approximated the frequency distribution for all traits in combination. Our results show that regional seed input can explain the more aggregated measures of local community structure, and some, but not all, aspects of community composition. This points to the possible importance of other (untested) processes and traits (e.g., dispersal vectors) operating at the local scale. Our modelling framework can readily allow new factors to be systematically investigated, which is a major advantage compared to previous simulation studies, as it allows us to find structurally realistic models, which can address questions pertinent to ecological theory and to conservation management.
Conformational changes associated with the assembly of recombinant ;2-microglobulin in vitro under acidic conditions were investigated using infrared spectroscopy and static and dynamic light scattering. In parallel, the morphology of the different aggregated species obtained under defined conditions was characterized by electron microscopy. The initial salt-induced aggregate form of ;2-microglobulin, composed of small oligomers (dimers to tetramers), revealed the presence of ;-strands organized in an intramolecular-like fashion. Further particle growth was accompanied by the formation of intermolecular ;-sheet structure and led to short curved forms. An increase in temperature by only 25 °C was able to disaggregate these assemblies, followed by the formation of longer filamentous structures. In contrast, a rise in temperature up to 100 °C was associated with a reorganization of the short curved forms at the level of secondary structure and the state of assembly, leading to a species with a characteristic infrared spectrum different from those of all the other aggregates observed before, suggesting a unique overall structure. The infrared spectral features of this species were nearly identical to those of ;2-microglobulin assemblies formed at low ionic strength with agitation, indicating the presence of fibrils, which was confirmed by electron microscopy. The observed spectroscopic changes suggest that the heat-triggered conversion of the short curved assemblies into fibrils involves a reorganization of the ;-strands from an antiparallel arrangement to a parallel arrangement, with the latter being characteristic of amyloid fibrils of ;2-microglobulin.
In this paper we report the results of an elicited imitation task on dative case marking in non-canonical double object constructions with 22 German children (3;9-6;8). The aim was to test the proficiency of the children's grammar and to see which strategies they use to produce ditransitive sentences in which the direct object precedes the indirect object. The analysis of the children's utterances/imitations shows that the animacy of the direct object affects the overt dative case marking of the indirect object. Children made more errors repeating dative case marking when the direct object was inanimate, i.e., they produced the accusative case on the indirect object (non-adult-like). When both objects were animate, children correctly produced the dative case on the indirect object. We describe and account for these performance strategies of the children in the framework of Optimality Theory. Assuming that the same universal constraints are at work as in the adult grammar, the difference between adults and children lies in the constraint ranking. We focus on a prominent pattern found in children's performance, which is absent (or rather oppressed) in the corresponding adult performance, and show that one and the same grammar accounts for both (in the sense of "strong continuity"). (c) 2007 Elsevier B.V. All rights reserved.
Multiplexed diagnostics and spectroscopic ruler applications with terbium to quantum dots FRET
(2008)
Editorial
(2008)
This study investigated whether older adults could acquire the ability to perform 2 cognitive operations in parallel in a paradigm in which young adults had been shown to be able to do so (K. Oberauer & R. Kliegl, 2004). Twelve young and 12 older adults practiced a numerical and a visuospatial continuous memory updating task in single-task and dual-task conditions for 16 to 24 sessions. After practice, 9 young adults were able to process the 2 tasks without dual- task costs, but none of the older adults had reached the criterion of parallel processing. The results suggest a qualitative difference between young and older adults in how they approach dual-task situations.
The quantification of phosphate bound to the C6 and C3 positions of glucose residues in starch has received increasing interest since the importance of starch phosphorylation for plant metabolism was discovered. The method described here is based on the observation that the isobaric compounds glucose-6-phosphate (Glc6P) and glucose-3- phosphate (Glc3P) exhibit significantly different fragmentation patterns in negative ion electrospray tandem mass spectrometry (MS/MS). A simple experiment involving collision-induced dissociation (CID) MS2 spectra of the sample and the two reference substances Glc3P and Glc6P permitted the quantification of the relative amounts of the two compounds in monosaccharide mixtures generated by acid hydrolysis of starch. The method was tested on well-characterized potato tuber starch. The results are consistent with those obtained by NMR analysis. In contrast to NMR, however, the presented method is fast and can be performed on less than 1 mg of starch. Starch samples of other origins exhibiting a variety of phosphorylation degrees were analyzed to assess the sensitivity and robustness of the method.
Introduction
(2008)
Through the cyclization of 1-(;-hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline and 1-(;- hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline with formaldehyde, phosgene, p-nitrobenzaldehyde or p-chlorophenyl isothiocyanate, 8-substituted 10,11-dihydro-8H,15bH-naphth[1,2-e][1,3]oxazino[4,3-a]isoquinolines (3 and 4) and 10,11- dihydro-8H,15bH-naphth[2,1-e][1,3]oxazino[4,3-a]isoquinolines (15 and 16) were prepared. Conformational analysis of both the piperidine and the 1,3-oxazine moieties of these heterocycles by NMR spectroscopy and an accompanying theoretical study revealed that these two conformationally flexible six-membered ring moieties prefer twisted chair conformers.
pH sensing in living cells represents one of the most prominent topics in biochemistry and physiology. In this study we performed one-photon and two-photon time-domain fluorescence lifetime imaging with a laser-scanning microscope using the time-correlated single-photon counting technique for imaging intracellular pH levels. The suitability of different commercial fluorescence dyes for lifetime-based pH sensing is discussed on the basis of in vitro as well of in situ measurements. Although the tested dyes are suitable for intensity-based ratiometric measurements, for lifetime- based techniques in the time-domain so far only BCECF seems to meet the requirements of reliable intracellular pH recordings in living cells.
Plant population modelling has been around since the 1970s, providing a valuable approach to understanding plant ecology from a mechanistic standpoint. It is surprising then that this area of research has not grown in prominence with respect to other approaches employed in modelling plant systems. In this review, we provide an analysis of the development and role of modelling in the field of plant population biology through an exploration of where it has been, where it is now and, in our opinion, where it should be headed. We focus, in particular, on the role plant population modelling could play in ecological forecasting, an urgent need given current rates of regional and global environmental change. We suggest that a critical element limiting the current application of plant population modelling in environmental research is the trade-off between the necessary resolution and detail required to accurately characterize ecological dynamics pitted against the goal of generality, particularly at broad spatial scales. In addition to suggestions how to overcome the current shortcoming of data on the process-level we discuss two emerging strategies that may offer a way to overcome the described limitation: (1) application of a modern approach to spatial scaling from local processes to broader levels of interaction and (2) plant functional-type modelling. Finally we outline what we believe to be needed in developing these approaches towards a 'science of forecasting'.
We have developed a microfluidic mixer optimized for rapid measurements of protein folding kinetics using synchrotron radiation circular dichroism (SRCD) spectroscopy. The combination of fabrication in fused silica and synchrotron radiation allows measurements at wavelengths below 220 nm, the typical limit of commercial instrumentation. At these wavelengths, the discrimination between the different types of protein secondary structure increases sharply. The device was optimized for rapid mixing at moderate sample consumption by employing a serpentine channel design, resulting in a dead time of less than 200 ;s. Here, we discuss the design and fabrication of the mixer and quantify the mixing efficiency using wide-field and confocal epi-fluorescence microscopy. We demonstrate the performance of the device in SRCD measurements of the folding kinetics of cytochrome c, a small, fast-folding protein. Our results show that the combination of SRCD with microfluidic mixing opens new possibilities for investigating rapid conformational changes in biological macromolecules that have previously been inaccessible.
Sequence learning at optimal stimulus-response mapping : evidence from a serial reaction-time task
(2008)
We propose a new version of the serial reaction time (SRT) task in which participants merely looked at the target instead of responding manually. As response locations were identical to target locations, stimulus - response compatibility was maximal in this task. We demonstrated that saccadic response times decreased during training and increased again when a new sequence was presented. It is unlikely that this effect was caused by stimulus - response (S - R) learning because bonds between (visual) stimuli and (oculomotor) responses were already well established before the experiment started. Thus, the finding shows that the building of S - R bonds is not essential for learning in the SRT task.
The through space NMR shielding (TSNMRS) values of adamantane, the 2(N + 1)2 spherical (4c, 2e) homoaromatic compounds 1,3-dehydro-5,7-adamantandiyl dication (C10H122+) and 1,3-dehydro-5,7-cubandiyl dication (C8H42+), and the (6c, 8e) homoaromatic compound 2,2;,4,4;,6,6;,8,8;,10,10;-dehydroadamantane tetracation (C10H44+) have been ab initio calculated, employing the NICS concept, and visualized as iso-chemical shielding surfaces (ICSSs). TSNMRS values can be successfully employed to study both the endohedral and exohedral aromaticity/ antiaromaticity of the compounds studied.
Quantification of the (Anti)Aromaticity of Fulvalenes Subjected to -Electron Cross-Delocalization
(2008)
Fulvalenes 3-12 were theoretically studied at the ab initio level of theory. For the global minima structures, the occupation of the bonding (pi)C=C orbital of the interring C=C double bond obtained by NBO analysis quantitatively proves pi-electron cross-delocalization resulting in, at least partially, 2- or 6pi-electron aromaticity and 8pi- electron antiaromaticity for appropriate moieties. The cross-conjugation was quantified by the corresponding occupation numbers and lengths of the interring C=C double bonds, while the aromaticity or antiaromaticity due to cross- delocalization of the pi-electrons was visualized and quantified by through-space NMR shielding surfaces.
Together with the nonsubstituted reference compound, para-methoxy- and para-nitro cyclohexyl benzoates have been synthesized and their conformational equilibria studied by low temperature NMR spectroscopy and theoretical DFT calculations. The free energy differences ;G° between axial and equatorial conformers were examined with respect to polar substituent influences on the conformational equilibrium of O-mono-substituted cyclohexane.
Tria-, penta-, hepta- and nonafulvenes (1-4) have been studied theoretically at the MP2 ab initio level of theory. For the global minimum structures, the occupation of the bonding ;C=C orbital of the exocyclic C=C double bond, obtained by NBO analysis, quantitatively proves ;-electron delocalization which can reveal partial 2-, 6- and 10-;-electron aromaticity, and 4-, 8- and 12-;-electron antiaromaticity of the ring moieties. Beside the corresponding occupation number, this conjugation was quantified by the length of the exocyclic C=C double bond whilst the (anti)aromaticity of the ring moieties of 1-4 was visualized and quantified by through space NMR shielding surfaces (TSNMRS).
Endohedral and external through-space NMR shieldings (TSNMRS) and the magnetic susceptibilities of the fullerene carbon cages of C50, C60, C60-6, C70, and C70-6 were assessed by ab initio molecular orbital calculations. Employing the nucleus-independent chemical shift (NICS) concept, these TSNMRS were visualized as isochemical shielding surfaces (ICSS) and were applied to quantitatively estimate either the aromaticity or the anti-aromaticity on the fullerene surface pertaining to the five- or six-membered ring moieties and the shielding of any nuclei enclosed within the carbon cages. Differences between the NICSs calculated at the center of the fullerene carbon cages and the experimental chemical shifts of encapsulated NMR-active nuclei as well as experimental shieldings observed for different encapsulated nuclei were able to be understood readily for the first time.
The through space NMR shielding (TSNMRS) values of two tricyclobutabenzene (TCBB) derivatives 2, of the corresponding hexamethylene and hexaoxo TCBB derivatives 3, of [4n]annuleno[4n + 2]annulene 5 and of its tricyclobutadiene parent compound 4 have been ab initio calculated by the GIAO perturbation method employing the nucleus- independent chemical shift (NICS) concept of Paul von Ragué Schleyer, and visualized as iso-chemical shielding surfaces (ICSS). TSNMRS values can be successfully employed to quantify and visualize the aromaticity of the central, and in 5 also of the terminal benzene ring moieties.
The push-pull character of a series of para-phenyl substituted isophorone chromophores has been quantified by the 13C chemical shift difference of the three conjugated partial C=C double bonds and the quotient of the occupations of both the bonding and anti-bonding orbitals of these C=C double bonds as well. The correlations of the two push-pull quantifying parameters, and to the corresponding bond lengths, strongly recommend ;*c=c/ ;c=c as the general parameter to estimate charge alternation and as a very useful indication of the molecular hyperpolarizabilities for NLO application of the compounds studied.