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Veränderung der Abflüsse
(2005)
The effect of oxygen plasma treatment and/or silanization with hexamethyldisilazane (HMDS) on the surface chemistry and the morphology of the SiO2-gate insulator were studied with respect to the performance of organic field effect transistors. Using X-ray photoelectron spectroscopy (XPS), it is shown that silanization leads to the growth of a polysiloxane interfacial layer and that longer silanization times increase the thickness of this layer. Most important, silanization reduces the signal from surface contaminations such as oxidized hydrocarbon molecules. In fact, the lowest concentration of these contaminations was found after a combined oxygen plasma/silanization treatment. The results of these investigations were correlated with the characteristic device parameters of polymer field effect transistors with poly(3-hexylthiophene)s as the semiconducting layer. We found that the field effect mobility correlates with the concentration of contaminations as measured by XPS. We, finally, demonstrate that silanization significantly improves the operational stability of the device in air compared to the untreated devices
Personalmanagement
(2005)
Personal als Erfolgspotential : Reformbedarf führt zur Professionalisierung von Personalabteilungen
(2005)
Teammanagement
(2005)
Humankapital
(2005)
Efficient refolding of proteins and prevention of their aggregation during folding are of vital importance in recombinant protein production and in finding cures for several diseases. We have used citrate synthase ( CS) as a model to understand the mechanism of aggregation during refolding and its prevention using several known structure-stabilizing cosolvent additives of the polyol series. Interestingly, no parallel correlation between the folding effect and the general stabilizing effect exerted by polyols was observed. Although increasing concentrations of polyols increased protein stability in general, the refolding yields for CS decreased at higher polyol concentrations, with erythritol reducing the folding yields at all concentrations tested. Among the various polyols used, glycerol was the most effective in enhancing the CS refolding yield, and a complete recovery of enzymatic activity was obtained at 7 M glycerol and 10 mu g/ml protein, a result superior to the action of the molecular chaperones GroEL and GroES in vitro. A good correlation between the refolding yields and the suppression of protein aggregation by glycerol was observed, with no aggregation detected at 7 M. The polyols prevented the aggregation of CS depending on the number of hydroxyl groups in them. Stopped-flow fluorescence kinetics experiments suggested that polyols, including glycerol, act very early in the refolding process, as no fast and slow phases were detectable. The results conclusively demonstrate that both the thermodynamic and kinetic aspects are critical in the folding process and that all structure-stabilizing molecules need not always help in productive folding to the native state. These findings are important for the rational design of small molecules for efficient refolding of various aggregation-prone proteins of commercial and medical relevance
The glycosphingolipid globoside (globotetraosylceramide, Gb4Cer) has been proposed to be the cellular receptor of human parvovirus B19. Quantitative measurements of the binding of parvovirus B19 to Gb4Cer were performed to explore the molecular basis of the virus tropism. Solid-phase assays with fluorescence-labeled liposomes or (125)iodine-labeled empty capsids were used to characterize the specificity of binding. In addition, surface plasmon resonance on lipid layers, as well as isothermal titration microcalorimetry, was utilized for real-time analysis of the virus-receptor interaction. These studies did not confirm binding of Gb4Cer to recombinant B19 VP2 capsids, suggesting that Gb4Cer does not function on its own as the cellular receptor of human parvovirus B19, but might be involved in a more complex recognition event. The biochemical results were further confirmed by cryo-electron microscopy image reconstructions at 10 A resolution, in which the structures of empty capsids were compared with empty capsids incubated with Gb4Cer. (C) 2004 Elsevier Inc. All rights reserved
Grundlagen digitaler Systeme
(2005)
Goethe und das Forstwesen : amtliche Tätigkeit, persönliche Erlebnisse und künstlerische Reflexe
(2005)
Bibliomanie
(2005)
Anatomie
(2005)
We report on polymer blend solar cells with an external quantum efficiency of more than 30% and a hi-h overall energy conversion efficiency (ECE) under white light illumination (100 mW/cm(2)) Of Lip to 1.7% using a blend of M3EH- PPV (poly [2,5-dimethoxy-1,4-phenylene-1,2-ethenylene-2-methoxy-5(2-ethylhexyloxy)-(1,4-pheiiylene-1,2-ethenylene)]) and CN-ether-PPV (poly[oxa-1,4-phenylene-1,2(1-cyano)ethenylene-2,5-dioctyloxy-1,4-phenylene-1,2-(2-cyano)ethellyiene-1,4- phenylene]). We attribute these high efficiencies to the formation of a vertically composition graded structure during spin coating Photoluminescence measurements performed on the blend layers indicated the formation of exciplexes between both types of polymers, which we propose to be one factor preventing even higher efficiencies
Diyne-containing poly(p-phenylene-vinylene)s, 4a-d, of general chemical structure-(Ph-C&3bond; C-C&3bond; C-Ph- CH&3bond; CH-Ph-CH&3bond; CH-)(n), obtained through polycondensation reactions of 1,4-bis(4-formyl-2,5-dioctyloxyphenyl)- buta-1,3-diyne (2) with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 3a-d, are the subject of this report. The polymers exhibit great disparity in their degree of polymerization, n, which might be ascribed to side-chain-related differences in reactivity of the reactive species during the polycondensation process and which led to n-dependent absorption (solution and solid state) and emission (solution) behaviors of the polymers. Polarizing optical microscopy and differential scanning calorimetry are employed to probe their thermal behavior. The structure is investigated by means of wide-angle X-ray diffraction for both isotropic and macroscopically oriented samples. Comparison of photophysical (experimental and theoretical) and electrochemical properties of the polymers with those of their yne- containing counterparts 6a-d [-(Ph-C&3bond; C-Ph-CH&3bond; CH-Ph-CH&3bond; CH-)(n)] has been carried out. Similar photophysical behavior was observed for both types of polymers despite the difference in backbone conjugation pattern. The introduction of a second yne unit in 4 lowers the HOMO and LUMO levels, thereby enhancing the electron affinity of polymers 4 compared to polymers 6. The "wider opening" introduced by the second yne unit facilitates moreover the movement of charges during the electrochemical processes leading to minimal discrepancy, Delta E-g between the optical and electrochemical band gap energies. Polymers 6, in contrast, show significant side-chain-dependent Delta E-g values. Low turn-on voltages between 2 and 3 V and maximal luminous efficiencies between 0.32 and 1.25 cd/A were obtained from LED devices of configuration ITO/PEDOT:PSS/polymer 4/Ca/Al
This contribution reports the combined influences of odd-even effects and the specific positioning of alkoxy side chains OR1 = (OCn+H-10(2(n+10)+1)) and OR2 = (OCnH2n+1) (with n = 6, 7, 8, 9) on the phenylene-ethynylene and phenylene- vinylene segments, respectively, on the optical properties of hybrid polymers P(n+10)/n of general repeating unit: -Ph-C equivalent to C-Ph-C equivalent to C-Ph-CH=CH-Ph-CH=CH-. For the polymeric materials, visual color impression varies alternatively between orange red (P16/6 and P18/8) and yellow (P17/7 and P19/9) according to the odd and even features of the alkoxy side chains, where odd or even relates to the total number of sp(3)-hybridized atoms within the side chains. This side chain related effect is ascribed to both absorptive and emissive behaviors of the polymers on the basis of photophysical investigations in the bulk. Almost identical thin film absorption spectra were obtained for all four materials; however, the photoluminescence of the odd polymers, P16/6 (lambda(f) = 556 nm) and P18/ 8 (lambda(f) = 614 nm), was red-shifted relative to that of their even counterparts (lambda(f) = 535 nm). Further, the P18/8 maximum at 614 nm can be readily assigned to excimer emission, as evidenced by the largest Stokes shift (5600 cm(- 1)), largest fwhmf-value (3700 cm(-1))(,) and the lowest Phi(f)-value of 24%. The strong pi-pi interchain interaction in P18/8, due to loose alkoxy side chains packing, does not only favor fluorescence quenching but also enable an effective inter- as well as intra-molecular recombination of the generated positive and negative polarons in electrolurninescence, which explains the good EL properties of this polymer irrespective of the solvent used. A voltage-dependent blue shift of the EL spectra of up to 100 nm was observed for P18/8 devices prepared from aromatic solvents. This red to green EL shift as observed with increasing voltage is assigned to conformational changes of the polymer chains with increasing temperature
Composite ground-motion models and logic trees: Methodology, sensitivities, and uncertainties
(2005)
Logic trees have become a popular tool in seismic hazard studies. Commonly, the models corresponding to the end branches of the complete logic tree in a probabalistic seismic hazard analysis (PSHA) are treated separately until the final calculation of the set of hazard curves. This comes at the price that information regarding sensitivities and uncertainties in the ground-motion sections of the logic tree are only obtainable after disaggregation. Furthermore, from this end-branch model perspective even the designers of the logic tree cannot directly tell what ground-motion scenarios most likely would result from their logic trees for a given earthquake at a particular distance, nor how uncertain these scenarios might be or how they would be affected by the choices of the hazard analyst. On the other hand, all this information is already implicitly present in the logic tree. Therefore, with the ground-motion perspective that we propose in the present article, we treat the ground-motion sections of a complete logic tree for seismic hazard as a single composite model representing the complete state-of-knowledge-and-belief of a particular analyst on ground motion in a particular target region. We implement this view by resampling the ground-motion models represented in the ground-motion sections of the logic tree by Monte Carlo simulation (separately for the median values and the sigma values) and then recombining the sets of simulated values in proportion to their logic-tree branch weights. The quantiles of this resampled composite model provide the hazard analyst and the decision maker with a simple, clear, and quantitative representation of the overall physical meaning of the ground-motion section of a logic tree and the accompanying epistemic uncertainty. Quantiles of the composite model also provide an easy way to analyze the sensitivities and uncertainties related to a given logic-tree model. We illustrate this for a composite ground- motion model for central Europe. Further potential fields of applications are seen wherever individual best estimates of ground motion have to be derived from a set of candidate models, for example, for hazard rnaps, sensitivity studies, or for modeling scenario earthquakes
The PEGASOS project was a major international seismic hazard study, one of the largest ever conducted anywhere in the world, to assess seismic hazard at four nuclear power plant sites in Switzerland. Before the report of this project has become publicly available, a paper attacking both methodology and results has appeared. Since the general scientific readership may have difficulty in assessing this attack in the absence of the report being attacked, we supply a response in the present paper. The bulk of the attack, besides some misconceived arguments about the role of uncertainties in seismic hazard analysis, is carried by some exercises that purport to be validation exercises. In practice, they are no such thing; they are merely independent sets of hazard calculations based on varying assumptions and procedures, often rather questionable, which come up with various different answers which have no particular significance. (C) 2005 Elsevier B.V. All rights reserved
It is well known that the performance of solar cells based on a blend of hole-accepting and electron-accepting conjugated polymers as the active material depend crucially on the length scale of the resulting phase separated morphology. However, a direct control of this morphology is difficult if the layer is prepared from an organic solvent. To circumvent this difficulty, recently a universal method to fabricate defined nano-structured blend layer using nanoparticles dispersed in water was demonstrated. These nanoparticles were prepared with the miniemulsion method, which allows for the preparation of semiconducting polymer nanospheres (SPNs) with diameters in the range of 30 to 300 nanometres. Since the process starts from the active material dissolved in a common solvent, it can be applied to the fabrication of nanoparticles of blends of polymers with oligomers or even with inorganic materials. We present here for the first time scanning near field optical microscopy (SNOM) investigations on these novel nanostructured polymer layers. We show that by spin-coating a mixture of two different dispersions a nanoparticle monolayer with a statistically distribution of the nanoparticles can be obtained. Mixing conjugated polymer nanoparticles with some inert particles like polystyrene beads may allow for the preparation of nano-sized light emitters
Microseismic data from observatories in Europe, which have been continuously recorded since about 100 years, contain information on the wave-climate in the North Atlantic. They can potentially be used as additional constraints in high-resolution temporal and spatial reconstructions of the storminess and oceanic waveheights in the past. To resolve spatial patterns data from observatories in different regions are needed. While previous recent studies analyzed only few observatory archives and relatively short time ranges, this is a first attempt to process the whole available data archive from different observatories. We correct and compare smoothed microseismic data from different stations and discuss their correlation and possible use for studies of storminess variability. Microseismic amplitudes at four seismic stations in northern Europe show amplitude peaks in 1920 and 1925, a slow decline in amplitudes till the middle of the 1930's followed by a steady increase of amplitudes till about 1990. From 1990 on microseismic amplitudes decrease. We find a good correlation between the average surface wind velocity in the North Atlantic and microseismic amplitudes at inland stations far away from the coast. Coastal stations are more influenced by local swell and are thus potentially useful to recover regional changes in wind and ocean wavefields with time. The study demonstrates that the analysis of microseismic has the potential to assess climate changes during the last 100 years
An increase in random molecular vibrations of a solid owing to heating above the melting point leads to a decrease in its long-range order and a loss of structural symmetry. Therefore conventional liquids are isotropic media. Here we report on a light-induced isothermal transition of a polymer film from an isotropic solid to an anisotropic liquid state in which the degree of mechanical anisotropy can be controlled by light. Whereas during irradiation by circular polarized light the film behaves as an isotropic viscoelastic fluid, it shows considerable fluidity only in the direction parallel to the light field vector under linear polarized light. The fluidization phenomenon is related to photoinduced motion of azobenzene-functionalized molecular units, which can be effectively activated only when their transition dipole moments are oriented close to the direction of the light polarization. We also describe here how the photofluidization allows nanoscopic elements of matter to be precisely manipulated
Photoinduced changes in the mechanical and dielectric properties of azobenzene polymer films were measured utilizing the method of electromechanical spectroscopy. The measurements revealed a strong correlation between the time- dependent behavior of the plate compliance and the dielectric constant under irradiation. Actinic light causes a light softening of the film that also manifests itself in the increase of the dielectric constant, whereas ultraviolet irradiation results in an initial plasticization of the film followed by its hardening. The latter is accompanied by decrease of the dielectric constant. A semiquantitative model based on the kinetics of the photoisomerization process in azobenzene polymers is proposed. We assume that both visible and ultraviolet irradiation increase the free volume in the layer due to photoisomerization. Additionally, ultraviolet light increases the modulus of the polymer matrix due to the presence of a high density of azobenzene moieties in the cis state. These assumptions allowed us to reproduce the time- dependent behavior of the bulk compliance as well as the dielectric constant at different irradiation intensities, for both visible and ultraviolet light, with only two adjustable parameters
The performance of highly soluble regioregular poly[ (3-hexylthiophene)-co-(3-octylthiophetie)] (P3HTOT) as a semiconducting material in organic field-effect transistors (OFETs) is presented in comparison to that of the corresponding homopolymers. Transistors made from as-prepared layers of P3HTOT exhibit a mobility of ca. 7 x 10(-3) cm(2) V-1 s(-1), which is comparable to the performance of transistors made from as-prepared poly(3-hexylthiophene) (P3HT) and almost 6 times larger than the mobility of transistors prepared with poly(3-octylthiophene) (P3OT). On the other hand, the solubility parameter delta(p) of P3HTOT is close to that of the highly soluble P3OT. Moreover, compared to a physical blend of poly(3-hexylthiophene) and poly(3-octylthiophene), the mobility of P3HTOT devices is almost twice as large and the performance does not degrade upon annealing at elevated temperatures. Therefore, the copolymer approach outlined here may be one promising step toward an optimum balance between a Sufficient processability of the polymers from common organic solvents, a high solid state order, and applicable OFET performances
Thermodynamic theory of light-induced material transport in amorphous azobenzene polymer films
(2005)
It was discovered 10 years ago that the exposure of an initially flat layer of an azobenzene-containing polymer to an inhomogeneous light pattern leads to the formation of surface relief structures, accompanied by a mass transport over several micrometers. However, the driving force of this process is still unclear. We propose a new thermodynamic approach that explains a number of experimental findings including the light-induced deformation of free-standing films and the formation of surface relief gratings for main inscription geometries. Our basic assumption is that under homogeneous illumination, an initially isotropic sample should stretch itself along the polarization direction to compensate the entropy decrease produced by the photoinduced reorientation of azobenzene chromophores. The magnitude of the elastic stress, estimated by taking the derivative of the free energy over the sample deformation, is shown to be sufficient to induce plastic deformation of the polymer film. Orientational distributions of chromophores predicted by our model are compared with those deduced from Raman intensity measurements
The luminescence of a ladder-type methyl-poly(para-phenylene) (MeLPPP) doped with platinum-porphyrin dye PtOEP covering the concentration 10(-3)-5% by weight has been measured employing cw and transient techniques. Upon excitation into the range of absorption of the host, strong phosphorescence of the dopant is observed. Possible ways of populating the dopant triplet state are considered. (c) 2004 Elsevier B.V. All rights reserved
In C-13 NMR spectroscopy, there are many empirical methods for fast and exact computation of C-13 chemical shifts; comparable procedures for Si-29 NMR chemical shifts are not existing or are older than 20 years. On basis of the largest database of Si-29 chemical shifts available, along this paper a relatively simple procedure for the similarly exact calculation of the Si-29 chemical shifts of disilanes (average margin of error ca. 3.7 ppm) is given. (c) 2005 Elsevier B.V. All rights reserved
Synthesis, characterisation and theoretical calculations of 2,6-diaminopurine etheno derivatives
(2005)
Four derivatives of 2,6-diaminopurine (1) were synthesised and characterised. When 1 was reacted with chloroacetaldehyde, 5-aminoimidazo[2,1- i] purine (2), 9-aminoimidazo[2,1-b]purine (3), 9-aminoimidazo[1,2- a]purine (4) and diimidazo[2,1-b: 2', 1'-i]purine (5) were formed. The purified products (3 - 5) were fully characterised by MS, complete NMR assignments as well as fluorescence and UV spectroscopy. The purified, isolated yields of these products ( 3 - 5) varied from 2.5 to 30%. The relative stability of different tautomers was investigated by theoretical calculations. Fluorescence characteristics are also discussed and compared to the starting material 1 and a reference molecule 2-aminopurine
In integrated medical considerations of the biological human system, both intellectual and motor performances in a similar manner are considered as a result of the function of the nervous system. Consequently, universal minimal dysfunctions of the central nervous system may lead to both intellectual and physical anomalies. Therefore, this study tests the hypothesis that there is a connection between the balance ability as a motor parameter and school success as an intellectual parameter. A postural measuring system based on the force-moment sensor technique was used to record the postural balance regulation of 773 children (circle divide 11 +/- 1 years). The school achievement of each child was determined by school grades. Data analysis was performed by linear as well as by nonlinear time series analyses. There are highly significant differences in balance regulation between good and poor pupils recognized by several linear and nonlinear parameters. Good pupils could be discriminated from pupils with bad results in learning to 80 %. The results support the hypothesis mentioned above. One possible explanation for the poor regulation of balance in bad learners could be a deficit in the neural maturity. In future, further developments will be targeted on higher discrimination levels, possibly in order to predict school success. On the other hand, the effects of special movement exercises on the neural development in childhood will be the focus in our further work