506 research outputs found
Palladium nanoparticles in catalytic carbon nanoreactors: the effect of confinement on Suzuki-Miyaura reactions
We explore the construction and performance of a range of catalytic nanoreactors based on palladium nanoparticles encapsulated in hollow graphitised nanofibres. The optimum catalytic material, with small palladium nanoparticles located almost exclusively at the graphitic step-edges within nanoreactors, exhibits attractive catalytic properties in Suzuki-Miyaura cross-coupling reactions. Confinement of nanoparticles at the step-edges facilitates retention of catalytic centres and recycling of catalytic nanoreactors without any significant loss of activity or selectivity over multiple catalytic cycles. Furthermore, careful comparison of the catalytic properties of palladium nanoparticles either on or in nanoreactors reveals that nanoscale confinement of catalysts fundamentally affects the pathways of the Suzuki-Miyaura reaction, with the yield and selectivity for the cross-coupled product critically dependent on the steric properties of the aryl iodide reactant, whereas no effects of confinement are observed for aryl boronic acid reactants possessing substituents in different positions. These results indicate that the oxidative addition step of the Suzuki-Miyaura reaction occurs at the step-edge of nanofibres, where the mechanisms and kinetics of chemical reactions are known to be sensitive to nanoscale confinement, and thus the extent of confinement in carbon nanoreactors can be discretely controlled by careful selection of the aryl iodide reactant
The Effect of Quantum Dot Shell Structure on Fluorescence Quenching By Acridine Ligand
The current strategy for the development of advanced methods of tumor treatment focuses on targeted drug delivery to tumor cells. Quantum dot (QD) - semiconductor fluorescent nanocrystal, conjugated with a pharmacological ligand, such as acridine, ensures real-time tracking of the delivery process of the active substance. However, the problem of QD fluorescence quenching caused by charge transfer can arise in the case when acridine is bound to the QD. We found that QD shell structure has a defining role on photoinduced electron transfer from QD on acridine ligand which leads to quenching of QD photoluminescence. We have found that multishell CdSe/ZnS/CdS/ZnS QD structure provides minimal reduction of photoluminescence quantum yield at minimal shell thickness compared to classical thin ZnS or “giant” shells. Thus, CdSe/ZnS/CdS/ZnS core/multishell QD could be an optimal choice for engineering of small-sized acridine-based fluorescent labels for tumor diagnosis and treatment systems.
Keywords: Quantum dot, photoluminescence quenching, DNA ligand, acridine derivative
Horizontal rotation signals detected by "G-Pisa" ring laser for the Mw=9.0, March 2011, Japan earthquake
We report the observation of the ground rotation induced by the Mw=9.0, 11th
of March 2011, Japan earthquake. The rotation measurements have been conducted
with a ring laser gyroscope operating in a vertical plane, thus detecting
rotations around the horizontal axis. Comparison of ground rotations with
vertical accelerations from a co-located force-balance accelerometer shows
excellent ring laser coupling at periods longer than 100s. Under the plane wave
assumption, we derive a theoretical relationship between horizontal rotation
and vertical acceleration for Rayleigh waves. Due to the oblique mounting of
the gyroscope with respect to the wave direction-of-arrival, apparent
velocities derived from the acceleration / rotation rate ratio are expected to
be always larger than, or equal to the true wave propagation velocity. This
hypothesis is confirmed through comparison with fundamental-mode, Rayleigh wave
phase velocities predicted for a standard Earth model.Comment: Accepted for publication in Journal of Seismolog
Influence of charged walls and defects on DC resistivity and dielectric relaxation in Cu-Cl boracite
Herbaceous angiosperms are not more vulnerable to drought-induced embolism than angiosperm trees
The water transport pipeline in herbs is assumed to be more vulnerable to drought than in trees due to the formation of frequent
embolisms (gas bubbles), which could be removed by the occurrence of root pressure, especially in grasses. Here, we studied
hydraulic failure in herbaceous angiosperms by measuring the pressure inducing 50% loss of hydraulic conductance (P50) in stems
of 26 species, mainly European grasses (Poaceae). Our measurements show a large range in P50 from 20.5 to 27.5 MPa, which
overlaps with 94% of the woody angiosperm species in a worldwide, published data set and which strongly correlates with an
aridity index. Moreover, the P50 values obtained were substantially more negative than the midday water potentials for five grass
species monitored throughout the entire growing season, suggesting that embolism formation and repair are not routine and
mainly occur under water deficits. These results show that both herbs and trees share the ability to withstand very negative water
potentials without considerable embolism formation in their xylem conduits during drought stress. In addition, structure-function
trade-offs in grass stems reveal that more resistant species are more lignified, which was confirmed for herbaceous and closely
related woody species of the daisy group (Asteraceae). Our findings could imply that herbs with more lignified stems will
become more abundant in future grasslands under more frequent and severe droughts, potentially resulting in lower forage
digestibility.
Desiccation and mortality dynamics in seedlings of different European beech (Fagus sylvatica L.) populations under extreme drought conditions
European beech (Fagus sylvatica L., hereafter beech), one of the major native tree species in Europe, is known to be drought sensitive. Thus, the identification of critical thresholds of drought impact intensity and duration are of high interest for assessing the adaptive potential of European beech to climate change in its native range. In a common garden experiment with one-year-old seedlings originating from central and marginal origins in six European countries (Denmark, Germany, France, Romania, Bosnia-Herzegovina, and Spain), we applied extreme drought stress and observed desiccation and mortality processes among the different populations and related them to plant water status (predawn water potential, 9PD) and soil hydraulic traits. For the lethal drought assessment, we used a critical threshold of soil water availability that is reached when 50% mortality in seedling populations occurs (LD50SWA). We found significant population differences in LD50SWA (10.5-17.8%), and mortality dynamics that suggest a genetic difference in drought resistance between populations. The LD50SWA values correlate significantly with the mean growing season precipitation at population origins, but not with the geographic margins of beech range. Thus, beech range marginality may be more due to climatic conditions than to geographic range. The outcome of this study suggests the genetic variation has a major influence on the varying adaptive potential of the investigated populations
Crack-Like Processes Governing the Onset of Frictional Slip
We perform real-time measurements of the net contact area between two blocks
of like material at the onset of frictional slip. We show that the process of
interface detachment, which immediately precedes the inception of frictional
sliding, is governed by three different types of detachment fronts. These
crack-like detachment fronts differ by both their propagation velocities and by
the amount of net contact surface reduction caused by their passage. The most
rapid fronts propagate at intersonic velocities but generate a negligible
reduction in contact area across the interface. Sub-Rayleigh fronts are
crack-like modes which propagate at velocities up to the Rayleigh wave speed,
VR, and give rise to an approximate 10% reduction in net contact area. The most
efficient contact area reduction (~20%) is precipitated by the passage of slow
detachment fronts. These fronts propagate at anomalously slow velocities, which
are over an order of magnitude lower than VR yet orders of magnitude higher
than other characteristic velocity scales such as either slip or loading
velocities. Slow fronts are generated, in conjunction with intersonic fronts,
by the sudden arrest of sub-Rayleigh fronts. No overall sliding of the
interface occurs until either of the slower two fronts traverses the entire
interface, and motion at the leading edge of the interface is initiated. Slip
at the trailing edge of the interface accompanies the motion of both the slow
and sub-Rayleigh fronts. We might expect these modes to be important in both
fault nucleation and earthquake dynamics.Comment: 19 page, 5 figures, to appear in International Journal of Fractur
Uniform Selection as a Primary Force Reducing Population Genetic Differentiation of Cavitation Resistance across a Species Range
Background: Cavitation resistance to water stress-induced embolism determines plant survival during drought. This adaptive trait has been described as highly variable in a wide range of tree species, but little is known about the extent of genetic and phenotypic variability within species. This information is essential to our understanding of the evolutionary forces that have shaped this trait, and for evaluation of its inclusion in breeding programs. Methodology: We assessed cavitation resistance (P 50), growth and carbon isotope composition in six Pinus pinaster populations in a provenance and progeny trial. We estimated the heritability of cavitation resistance and compared the distribution of neutral markers (FST) and quantitative genetic differentiation (QST), for retrospective identification of the evolutionary forces acting on these traits. Results/Discussion: In contrast to growth and carbon isotope composition, no population differentiation was found for cavitation resistance. Heritability was higher than for the other traits, with a low additive genetic variance (h 2 ns = 0.4360.18, CVA = 4.4%). QST was significantly lower than FST, indicating uniform selection for P50, rather than genetic drift. Putativ
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