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Molecularly imprinted polymer (MP) nanofilrns for transferrin (Trf) have been synthesized on gold surfaces by electro-polymerizing the functional monomer scopoletin in the presence of the protein target or around pre-adsorbed Trf. As determined by atomic force microscopy (AFM) the film thickness was comparable with the molecular dimension of the target. The target (re)binding properties of the electro-synthesized MIP films was evaluated by cyclic voltammetry (CV) and square wave voltammetry (SWV) through the target-binding induced permeability changes of the MIP nanofilms to the ferricyanide redox marker, as well as by surface plasmon resonance (SPR) and surface enhanced infrared absorption spectroscopy (SEIRAS) of the immobilized protein molecules. For Trf a linear concentration dependence in the lower micromolar range and an imprinting factor of similar to 5 was obtained by SWV and SPR. Furthermore, non-target proteins including the iron-free apo-Trf were discriminated by pronounced size and shape specificity. Whilst it is generally assumed that the rebinding of the target or of cross-reacting proteins exclusively takes place at the polymer here we considered also the interaction of the protein molecules with the underlying gold transducers. We demonstrate by SWV that adsorption of proteins suppresses the signal of the redox marker even at the bare gold surface and by SEIRAS that the treatment of the MIP with proteinase K or NaOH only partially removes the target protein. Therefore, we conclude that when interpreting binding of proteins to directly MIP-covered gold electrodes the interactions between the protein and the gold surface should also be considered.
Many studies of synchronization properties of coupled oscillators, based on the classical Kuramoto approach, focus on ensembles coupled via a mean field. Here we introduce a setup of Kuramoto-type phase oscillators coupled via two mean fields. We derive stability properties of the incoherent state and find traveling wave solutions with different locking patterns; stability properties of these waves are found numerically. Mostly nontrivial states appear when the two fields compete, i.e. one tends to synchronize oscillators while the other one desynchronizes them. Here we identify normal branches which bifurcate from the incoherent state in a usual way, and anomalous branches, appearance of which cannot be described as a bifurcation. Furthermore, hybrid branches combining properties of both are described. In the situations where no stable traveling wave exists, modulated quasiperiodic in time dynamics is observed. Our results indicate that a competition between two coupling channels can lead to a complex system behavior, providing a potential generalized framework for understanding of complex phenomena in natural oscillatory systems.
Increasing interests in hydrocarbon resources at depths have drawn greater attentions to the deeply-buried carbonate reservoirs in the Tarim Basin in China. In this study, the cyclic dolomite rocks of Upper Cambrian Lower Qiulitag Group from four outcrop sections in northwestern Tarim Basin were selected to investigate and evaluate the petrophysical properties in relation to depositional facies and cyclicity. The Lower Qiulitag Group includes ten lithofacies, which were deposited in intermediate to shallow subtidal, restricted shallow subtidal, intertidal, and supratidal environments on a carbonate ramp system. These lithofacies are vertically stacked into repeated shallowing-upward, meter-scale cycles which are further grouped into six third-order depositional sequences (Sq1 to Sq6). There are variable types of pore spaces in the Lower Qiulitag Group dolomite rocks, including interparticle, intraparticle, and fenestral pores of primary origin, inter crystal, and vuggy pores of late diagenetic modification. The porosity in the dolomites is generally facies-selective as that the microbially-originated thrombolites and stromatolites generally yield a relatively high porosity. In contrast, the high-energy ooidal grainstones generally have very low porosity. In this case, the microbialite-based peritidal cycles and peritidal cycle-dominated highstand (or regressive) successions have relatively high volumes of pore spaces, although highly fluctuating (or vertical inhomogeneous). Accordingly, the grainstone-based subtidal cycles and subtidal cycle-dominated transgressive successions generally yield extremely low porosity. This scenario indicates that porosity development and preservation in the thick dolomite successions are primarily controlled by depositional facies which were influenced by sea-level fluctuations of different orders and later diagenetic overprinting.
The Gongjue basin from the eastern Qiangtang terrane is located in the transition region where the regional structural lineation curves from east-west-oriented in Tibet to north-south-oriented in Yunnan. In this study, we sampled the red beds in the basin from the lower Gongjue to upper Ranmugou formations for the first time covering the entire stratigraphic profile. The stratigraphic ages are bracketed within 53-43Ma by new detrital zircon U-Pb ages constraining the maximum deposition age to 52.51.5Ma. Rock magnetic and petrographic studies indicate that detrital magnetite and hematite are the magnetic carriers. Positive reversals and fold tests demonstrate that the characteristic remanent magnetization has a primary origin. The Gongjue and Ranmugou formations yield mean characteristic remanent magnetization directions of D-s/I-s=31.0 degrees/21.3 degrees and D-s/I-s=15.9 degrees/22.0 degrees, respectively. The magnetic inclination of these characteristic remanent magnetizations is significantly shallowed compared to the expected inclination for the locality. However, the elongation/inclination correction method does not provide a meaningful correction, likely because of syn-depositional rotation. Rotations relative to the Eurasian apparent polar wander path occurred in three stages: Stage I, 33.33.4 degrees clockwise rotation during the deposition of the Gongjue and lower Ranmugou formations; Stage II, 26.93.7 degrees counterclockwise rotation during deposition of the lower and middle Ranmugou formation; and Stage III, 17.73.3 degrees clockwise rotation after 43Ma. The complex rotation history recorded in the basin is possibly linked to sinistral shear along the Qiangtang block during India indentation into Asia and the early stage of the extrusion of the northwestern Indochina blocks away from eastern Tibet.
Paleogeographic reconstructions of terranes can greatly benefit from the provenance analysis of sediments. A series of Cenozoic basins provide key sedimentary archives for investigating the growth of the Tibetan Plateau, yet the provenance of the sediments in these basins has never been constrained robustly. Here we report sedimentary petrological and detrital zircon geochronological data from the Paleocene-Eocene Nangqian-Xialaxiu and Gongjue basins. Sandstone detrital modes and zircon morphology suggest that the samples collected in these two basins were sourced from recycled orogen. Detrital zircon geochronology indicates that sediments in the Nangqian-Xialaxiu Basin are characterized by two distinct age populations at 220-280 Ma and 405-445 Ma. In contrast, three predominant age populations of 207-256 Ma, 423-445 Ma, and 1851-1868 Ma, and two subordinate age populations of similar to 50 Ma and similar to 2500 Ma, are recognized in the Gongjue Basin. Comparison with detrital zircon ages from the surrounding terranes suggests that sediments in the Nangqian-Xialaxiu Basin come from the neighboring thrust belts, whereas sediments from the Gongjue Basin are predominantly derived from the distant Songpan-Ganzi Terrane with minor contribution from the surrounding areas. A three-stage Cenozoic evolution of the eastern Tibetan Plateau is proposed. During the Paleocene, the Nangqian-Xialaxiu Basin appeared as a set of small intermontane sub-basins and received plentiful sediments from the neighboring mountain belts; during the Eocene, the Gongjue Basin kept a relatively low altitude and was a depression at the edge of a proto-Plateau; since the Oligocene, the Tibetan Plateau further uplifted and the marginal Gongjue Basin was involved in the Tibetan interior orogeny, indicating the eastward propagation of the Tibetan Plateau.
The Upper Cambrian Lower Qiulitag Group in the Tarim Basin, NW China, is overwhelmingly composed of cyclic dolomites. Based on extensive field investigations and facies analysis from four outcrop sections in the Bachu-Keping area, northwestern Tarim Basin, four main types of facies are recognized: open-marine subtidal, restricted shallow subtidal, intertidal, and supratidal facies, and these are further subdivided into ten lithofacies. In general, these facies are vertically arranged into shallowing-upward, metre-scale cycles. These cycles are commonly composed of a thin basal horizon reflecting abrupt deepening, and a thicker upper succession showing gradual shallowing upwards. Based on the vertical facies arrangements and changes across boundary surfaces, two types of cycle: peritidal and shallow subtidal cycle, are further identified. The peritidal cycles, predominating over the lower-middle Lower Qiulitag Group, commence with shallow subtidal to lower intertidal facies and are capped by inter-supratidal facies. In contrast, the shallow subtidal cycles, dominating the upper Lower Qiulitag Group, are capped by shallow-subtidal facies. Based on vertical lithofacies variations, cycle stacking patterns, and accommodation variations revealed by Fischer plots, six larger-scale third-order depositional sequences (Sq1-Sq6) are recognized. These sequences generally consist of a lower transgressive and an upper regressive systems tract. The transgressive tracts are dominated by thicker-than-average cycles, indicating an overall accommodation increase, whereas the regressive tracts are characterized by thinner-than-average peritidal cycles, indicating an overall accommodation decrease. The sequence boundaries are characterized by transitional zones of stacked thinner-than-average cycles, rather than by a single surface. These sequences can further be grouped into lower-order sequence sets: the lower and upper sequence sets. The lower sequence set, including Sq1-Sq3, is characterized by peritidal facies-dominated sequences and a progressive decrease in accommodation space, indicating a longer-term fall in sea level. In contrast, the upper sequence set (Sq4-Sq6) is characterized by subtidal facies-dominated sequences and a progressive increase in accommodation space, indicating a longer-term rise in sea level.
Investigation of the TCA cycle and glycolytic metabolons and their physiological impacts in plants
(2016)
Although the use of stable transformation technology has led to great insight into gene function, its application in high-throughput studies remains arduous. Agro-infiltration have been widely used in species such as Nicotiana benthamiana for the rapid detection of gene expression and protein interaction analysis, but this technique does not work efficiently in other plant species, including Arabidopsis thaliana. As an efficient high-throughput transient expression system is currently lacking in the model plant species A. thaliana, we developed a method that is characterized by high efficiency, reproducibility, and suitability for transient expression of a variety of functional proteins in A. thaliana and 7 other plant species, including Brassica oleracea, Capsella rubella, Thellungiella salsuginea, Thellungiella halophila, Solanum tuberosum, Capsicum annuum, and N. benthamiana. Efficiency of this method was independently verified in three independent research facilities, pointing to the robustness of this technique. Furthermore, in addition to demonstrating the utility of this technique in a range of species, we also present a case study employing this method to assess protein-protein interactions in the sucrose biosynthesis pathway in Arabidopsis.
Changes in carbon flow and sink/source activities can affect floral, architectural, and reproductive traits of plants. In potato, overexpression (OE) of the purple acid phosphatase 2 of Arabidopsis (AtPAP2) resulted in earlier flowering, faster growth rate, increased tubers and tuber starch content, and higher photosynthesis rate. There was a significant change in sucrose, glucose and fructose levels in leaves, phloem and sink biomass of the OE lines, consistent with an increased expression of sucrose transporter 1 (StSUT1). Furthermore, the expression levels and enzyme activity of sucrose-phosphate synthase (SPS) were also significantly increased in the OE lines. These findings strongly suggest that higher carbon supply from the source and improved sink strength can improve potato tuber yield. (C) 2014 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.
RNA-based processes play key roles in the regulation of eukaryotic gene expression. This includes both the processing of pre-mRNAs into mature mRNAs ready for translation and RNA-based silencing processes, such as RNA-directed DNA methylation (RdDM). Polyadenylation of pre-mRNAs is one important step in their processing and is carried out by three functionally specialized canonical nuclear poly(A) polymerases in Arabidopsis thaliana. Null mutations in one of these, termed PAPS1, result in a male gametophytic defect. Using a fluorescence-labelling strategy, we have characterized this defect in more detail using RNA and small-RNA sequencing. In addition to global defects in the expression of pollen-differentiation genes, paps1 null-mutant pollen shows a strong overaccumulation of transposable element (TE) transcripts, yet a depletion of 21- and particularly 24-nucleotide-long short interfering RNAs (siRNAs) and microRNAs (miRNAs) targeting the corresponding TEs. Double-mutant analyses support a specific functional interaction between PAPS1 and components of the RdDM pathway, as evident from strong synergistic phenotypes in mutant combinations involving paps1, but not paps2 paps4, mutations. In particular, the double-mutant of paps1 and rna-dependent rna polymerase 6 (rdr6) shows a synergistic developmental phenotype disrupting the formation of the transmitting tract in the female gynoecium. Thus, our findings in A. thaliana uncover a potentially general link between canonical poly(A) polymerases as components of mRNA processing and RdDM, reflecting an analogous interaction in fission yeast.
Background/objective: Negative emotional states, such as depression, anxiety, and stress challenge health care due to their long-term consequences for mental disorders. Accumulating evidence indicates that regular physical activity (PA) can positively influence negative emotional states. Among possible candidates, resilience and exercise tolerance in particular have the potential to partly explain the positive effects of PA on negative emotional states. Thus, the aim of this study was to investigate the association between PA and negative emotional states, and further determine the mediating effects of exercise tolerance and resilience in such a relationship. Method: In total, 1117 Chinese college students (50.4% female, Mage=18.90, SD=1.25) completed a psychosocial battery, including the 21-item Depression Anxiety Stress Scale (DASS-21), the Connor-Davidson Resilience Scale (CD-RISC), the Preference for and Tolerance of the Intensity of Exercise Questionnaire (PRETIE-Q), and the International Physical Activity Questionnaire short form (IPAQ-SF). Regression analysis was used to identify the serial multiple mediation, controlling for gender, age and BMI. Results: PA, exercise intensity-tolerance, and resilience were significantly negatively correlated with negative emotional states (Ps<.05). Further, exercise tolerance and resilience partially mediated the relationship between PA and negative emotional states. Conclusions: Resilience and exercise intensity-tolerance can be achieved through regularly engaging in PA, and these newly observed variables play critical roles in prevention of mental illnesses, especially college students who face various challenges. Recommended amount of PA should be incorporated into curriculum or sport clubs within a campus environment.
To provide physically based wind modelling for wind erosion research at regional scale, a 3D computational fluid dynamics (CFD) wind model was developed. The model was programmed in C language based on the Navier-Stokes equations, and it is freely available as open source. Integrated with the spatial analysis and modelling tool (SAMT), the wind model has convenient input preparation and powerful output visualization. To validate the wind model, a series of experiments was conducted in a wind tunnel. A blocking inflow experiment was designed to test the performance of the model on simulation of basic fluid processes. A round obstacle experiment was designed to check if the model could simulate the influences of the obstacle on wind field. Results show that measured and simulated wind fields have high correlations, and the wind model can simulate both the basic processes of the wind and the influences of the obstacle on the wind field. These results show the high reliability of the wind model. A digital elevation model (DEM) of an area (3800 m long and 1700 m wide) in the Xilingele grassland in Inner Mongolia (autonomous region, China) was applied to the model, and a 3D wind field has been successfully generated. The clear implementation of the model and the adequate validation by wind tunnel experiments laid a solid foundation for the prediction and assessment of wind erosion at regional scale.
In order to identify the areas in the Xilingele grassland which are sensitive to wind erosion, a computational fluid dynamics model (CFD-WEM) was used to simulate the wind fields over a region of 37 km(2) which contains different topography and land use types. Previous studies revealed the important influences of topography and land use on wind erosion in the Xilingele grassland. Topography influences wind fields at large scale, and land use influences wind fields near the ground. Two steps were designed to implement the CFD wind simulation, and they were respectively to simulate the influence of topography and surface roughness on the wind. Digital elevation model (DEM) and surface roughness length were the key inputs for the CFD simulation. The wind simulation by CFD-WEM was validated by a wind data set which was measured simultaneously at six positions in the field. Three scenarios with different wind velocities were designed based on observed dust storm events, and wind fields were simulated according to these scenarios to predict the sensitive areas to wind erosion. General assumptions that cropland is the most sensitive area to wind erosion and heavily and moderately grazed grasslands are both sensitive etc. can be refined by the modelling of CFD-WEM. Aided by the results of this study, the land use planning and protection measures against wind erosion can be more efficient. Based on the case study in the Xilingele grassland, a method of regional wind erosion assessment aided by CFD wind simulation is summarized. The essence of this method is a combination of CFD wind simulation and determination of threshold wind velocity for wind erosion. Because of the physically-based simulation and the flexibility of the method, it can be generalised to other regions.
The open source computational fluid dynamics (CFD) wind model (CFD-WEM) for wind erosion research in the Xilingele grassland in Inner Mongolia (autonomous region, China) is compared with two open source CFD models Gerris and OpenFOAM. The evaluation of these models was made according to software technology, implemented methods, handling, accuracy and calculation speed. All models were applied to the same wind tunnel data set. Results show that the simplest CFD-WEM has the highest calculation speed with acceptable accuracy, and the most powerful OpenFOAM produces the simulation with highest accuracy and the lowest calculation speed. Gerris is between CFD-WEM and OpenFOAM. It calculates faster than OpenFOAM, and it is capable to solve different CFD problems. CFD-WEM is the optimal model to be further developed for wind erosion research in Inner Mongolia grassland considering its efficiency and the uncertainties of other input data. However, for other applications using CFD technology, Gerris and OpenFOAM can be good choices. This paper shows the powerful capability of open source CFD software in wind erosion study, and advocates more involvement of open source technology in wind erosion and related ecological researches.
The process of leaf senescence consists of the final stage of leaf development. It has evolved as a mechanism to degrade macromolecules and micronutrients and remobilize them to other developing parts of the plant; hence it plays a central role for the survival of plants and crop production. During senescence, a range of physiological, morphological, cellular, and molecular events occur, which are generally referred to as the senescence syndrome that includes several hallmarks such as visible yellowing, loss of chlorophyll and water content, increase of ion leakage and cell death, deformation of chloroplast and cell structure, as well as the upregulation of thousands of so-called senescence-associated genes (SAGs) and downregulation of photosynthesis-associated genes (PAGs). This chapter is devoted to methods characterizing the onset and progression of leaf senescence at the morphological, physiological, cellular, and molecular levels. Leaf senescence normally progresses in an age-dependent manner but is also induced prematurely by a variety of environmental stresses in plants. Focused on the hallmarks of the senescence syndrome, a series of protocols is described to asses quantitatively the senescence process caused by developmental cues or environmental perturbations. We first briefly describe the senescence process, the events associated with the senescence syndrome, and the theories and methods to phenotype senescence. Detailed protocols for monitoring senescence in planta and in vitro, using the whole plant and the detached leaf, respectively, are presented. For convenience, most of the protocols use the model plant species Arabidopsis and rice, but they can be easily extended to other plants.
Our study presents the results of a moment tensor inversion of 19 microseismic events with M-L between 2.0 and 3.4, associated with the stimulation operation of an enhanced geothermal reservoir in Basel, Switzerland, in 2006. We adopt a three-step procedure to retrieve point source solution parameters based on full waveform inversion. The inversion is performed by fitting displacement amplitude spectra and displacement seismograms in the first and second step, respectively, assuming a double couple source model and thus obtaining focal solutions for all 19 events. Our results are in agreement with focal mechanisms from a previous study, which employed P wave first-motion polarities from more than 40 stations, whereas our solutions are achieved using full waveform data recorded by less than 10 surface stations. In the last step, a full moment tensor inversion is performed. The results from the moment tensor inversion show an improvement on the waveform fitting compared to the double couple models, which is verified by an F-test. We investigate the stability of the moment tensor solutions by employing different velocity models. The isotropic components of the moment tensor solutions of some events are not negligible, suggesting source volume changes due to fluid injection. Events with significant isotropic components occurred mainly during the stimulation phase and close to the injection well. On the other hand, events that occurred in the post-stimulation phase are predominantly pure shear failure and located further away from the well bore. These spatio-temporal patterns can be explained by the influence of pore pressure variations during and after the hydraulic stimulation at the geothermal site. (C) 2014 Elsevier Ltd. All rights reserved.
Fast actuation speed, large-shape deformation and robust responsiveness are critical to synthetic soft actuators. A simultaneous optimization of all these aspects without trade-offs remains unresolved. Here we describe porous polymer actuators that bend in response to acetone vapour (24 kPa, 20 degrees C) at a speed of an order of magnitude faster than the state-of-the-art, coupled with a large-scale locomotion. They are meanwhile multi-responsive towards a variety of organic vapours in both the dry and wet states, thus distinctive from the traditional gel actuation systems that become inactive when dried. The actuator is easy-to-make and survives even after hydrothermal processing (200 degrees C, 24 h) and pressing-pressure (100 MPa) treatments. In addition, the beneficial responsiveness is transferable, being able to turn 'inert' objects into actuators through surface coating. This advanced actuator arises from the unique combination of porous morphology, gradient structure and the interaction between solvent molecules and actuator materials.
We present observations of three-dimensional magnetic power spectra in wavevector space to investigate the anisotropy and scalings of sub-Alfvenic solar wind turbulence at magnetohydrodynamic (MHD) scale using the Magnetospheric Multiscale spacecraft. The magnetic power distributions are organized in a new coordinate determined by wavevectors ((kappa) over cap) and background magnetic field ((b) over cap (0)) in Fourier space. This study utilizes two approaches to determine wavevectors: the singular value decomposition method and multispacecraft timing analysis. The combination of the two methods allows an examination of the properties of magnetic field fluctuations in terms of mode compositions without any spatiotemporal hypothesis. Observations show that fluctuations (delta B-perpendicular to 1) in the direction perpendicular to (kappa) over cap and (b) over cap (0) prominently cascade perpendicular to (b) over cap (0), and such anisotropy increases with wavenumbers. The reduced power spectra of 6.8 11 follow Goldreich-Sridhar scalings: (P) over cap (k(perpendicular to)) proportional to k(perpendicular to)(-5/3) and (P) over cap (k(parallel to)) proportional to k(parallel to)(-2). In contrast, fluctuations within the (k) over cap(b) over cap (0) plane show isotropic behaviors: perpendicular power distributions are approximately the same as parallel distributions. The reduced power spectra of fluctuations within the (k) over cap(b) over cap (0) plane follow the scalings (P) over cap (k(perpendicular to)) proportional to k(perpendicular to)(-3/2) and (P) over cap (k(parallel to)) proportional to k(parallel to)(-3/2). Comparing frequency-wavevector spectra with theoretical dispersion relations of MHD modes, we find that delta B-perpendicular to 1 are probably associated with Alfven modes. On the other hand, magnetic field fluctuations within the (k) over cap(b) over cap (0) plane more likely originate from fast modes based on their isotropic behaviors. The observations of anisotropy and scalings of different magnetic field components are consistent with the predictions of current compressible MHD theory. Moreover, for the Alfvenic component, the ratio of cascading time to the wave period is found to be a factor of a few, consistent with critical balance in the strong turbulence regime. These results are valuable for further studies of energy compositions of plasma turbulence and their effects on energetic particle transport.
We use a data set of 35 surface pollen samples from lake sediments, moss polsters and top soils on the north- eastern Tibetan Plateau to explore the relationship between modern pollen assemblages and contemporary vegetation patterns. The surface pollen transect spanned four vegetation zones--alpine meadow, steppe, steppe desert and desert-- under different climatic/elevational conditions. Relative representation (R (rel)) values and Principal Components Analysis (PCA) were used to determine the relationships between modern pollen and vegetation and regional climate gradients. The results show that the main vegetation zones along the regional and elevational transects can be distinguished by their modern pollen spectra. Relative to Poaceae, a high representation of Artemisia, Nitraria and Chenopodiaceae was found, while Cyperaceae and Gentiana showed values in the middle range, and Ranunculaceae, Asteraceae, Ephedra and Fabaceae had low relative representation values. PCA results indicate a high correlation between the biogeoclimatic zones and annual precipitation and annual temperature and July temperature. The Artemisia/ Chenopodiaceae ratio and the Artemisia/Cyperaceae ratio are useful tools for qualitative and semi-quantitative palaeoenvironmental reconstruction on the north-eastern Tibetan Plateau. Surface lake sediments are found to have different palynomorph spectra from moss cushion and soil samples, reflecting the larger pollen source area in the contemporary vegetation for lakes.
This thesis focuses on the synthesis of novel functional materials based on plasmonic nanoparticles. Three systems with targeted surface modification and functionalization have been designed and synthesized, involving modified perylenediimide doped silica-coated silver nanowires, polydopamine or TiO2 coated gold-palladium nanorods and thiolated poly(ethylene glycol) (PEG-SH)/dodecanethiol (DDT) modified silver nanospheres. Their possible applications as plasmonic resonators, chiral sensors as well as photo-catalysts have been studied. In addition, the interaction between silver nanospheres and 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) molecules has also been investigated in detail.
In the first part of the thesis, surface modification on Ag nanowires (NWs) with optimized silica coating through a modified Stöber method has been firstly conducted, employing sodium hydroxide (NaOH) to replace ammonia solution (NH4OH). The coated silver nanowires with a smooth silica shell have been investigated by single-particle dark-field scattering spectroscopy, transmission electron microscopy and electron-energy loss spectroscopy to characterize the morphologies and structural components. The silica-coated silver nanowires can be further functionalized with fluorescent molecules in the silica shell via a facile one-step coating method. The as-synthesized nanowire is further coupled with a gold nanosphere by spin-coating for the application of the sub-diffractional chiral sensor for the first time. The exciton-plasmon-photon interconversion in the system eases the signal detection in the perfectly matched 1D nanostructure and contributes to the high contrast of the subwavelength chiral sensing for the polarized light.
In the second part of the thesis, dumbbell-shaped Au-Pd nanorods coated with a layer of polydopamine (PDA) or titanium dioxide (TiO2) have been constructed. The PDA- and TiO2- coated Au-Pd nanorods show a strong photothermal conversion performance under NIR illumination. Moreover, the catalytic performance of the particles has been investigated using the reduction of 4-nitrophenol (4-NP) as the model reaction. Under light irradiation, the PDA-coated Au-Pd nanorods exhibit a superior catalytic activity by increasing the reaction rate constant of 3 times. The Arrhenius-like behavior of the reaction with similar activation energies in the presence and absence of light irradiation indicates the photoheating effect to be the dominant mechanism of the reaction acceleration. Thus, we attribute the enhanced performance of the catalysis to the strong photothermal effect that is driven by the optical excitation of the gold surface plasmon as well as the synergy with the PDA layer.
In the third part, the kinetic study on the adsorption of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquino-dimethane (F4TCNQ) on the surface of Ag nanoparticles (Ag NPs) in chloroform has been reported in detail. Based on the results obtained from the UV-vis-NIR absorption spectroscopy, cryogenic transmission electron microscopy (cryo-TEM), scanning nano-beam electron diffraction (NBED) and electron energy loss spectroscopy (EELS), a two-step interaction kinetics has been proposed for the Ag NPs and F4TCNQ molecules. It includes the first step of electron transfer from Ag NPs to F4TCNQ indicated by the ionization of F4TCNQ, and the second step of the formation of Ag-F4TCNQ complex. The whole process has been followed via UV-vis-NIR absorption spectroscopy, which reveals distinct kinetics at two stages: the instantaneous ionization and the long-term complex formation. The kinetics and the influence of the molar ratio of Ag NPs/F4TCNQ molecules on the interaction between Ag NPs and F4TCNQ molecules in the organic solution are reported herein for the first time. Furthermore, the control experiment with silica-coated Ag NPs indicates that the charge transfer at the surface between Ag NPs and F4TCNQ molecules has been prohibited by a silica layer of 18 nm.
In this study, the kinetics of the adsorption of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ) on the surface of Ag nanoparticles (Ag NPs) in chloroform has been intensively investigated, as molecular doping is known to play a crucial role in organic electronic devices. Based on the results obtained from UV-visible (vis)-near-infrared (NIR) absorption spectroscopy, cryogenic transmission electron microscopy, scanning nanobeam electron diffraction, and electron energy loss spectroscopy, a two-step interaction kinetics has been proposed for the Ag NPs and F(4)TCNQ molecules, which includes the first step of electron transfer from Ag NPs to F(4)TCNQ indicated by the ionization of F(4)TCNQ and the second step of the formation of a Ag-F(4)TCNQ complex. The whole process has been followed via UV-vis-NIR absorption spectroscopy, which reveals distinct kinetics at two stages: the instantaneous ionization and the long-term complex formation. The kinetics and the influence of the molar ratio of Ag NPs/F(4)TCNQ molecules on the interaction between Ag NPs and F(4)TCNQ molecules in an organic solution are reported herein for the first time. Furthermore, the control experiment with silica-coated Ag NPs manifests that the charge transfer at the surface between Ag NPs and F(4)TCNQ molecules is prohibited by a silica layer of 18 nm.
Bimetallic nanostructures comprising plasmonic and catalytic components have recently emerged as a promising approach to generate a new type of photo-enhanced nanoreactors. Most designs however concentrate on plasmon-induced charge separation, leaving photo-generated heat as a side product.
This work presents a photoreactor based on Au-Pd nanorods with an optimized photothermal conversion, which aims to effectively utilize the photo-generated heat to increase the rate of Pd-catalyzed reactions. Dumbbell-shaped Au nanorods were fabricated via a seed-mediated growth method using binary surfactants. Pd clusters were selectively grown at the tips of the Au nanorods, using the zeta potential as a new synthetic parameter to indicate the surfactant remaining on the nanorod surface.
The photothermal conversion of the Au-Pd nanorods was improved with a thin layer of polydopamine (PDA) or TiO2.
As a result, a 60% higher temperature increment of the dispersion compared to that for bare Au rods at the same light intensity and particle density could be achieved.
The catalytic performance of the coated particles was then tested using the reduction of 4-nitrophenol as the model reaction. Under light, the PDA-coated Au-Pd nanorods exhibited an improved catalytic activity, increasing the reaction rate by a factor 3.
An analysis of the activation energy confirmed the photoheating effect to be the dominant mechanism accelerating the reaction. Thus, the increased photothermal heating is responsible for the reaction acceleration.
Interestingly, the same analysis shows a roughly 10% higher reaction rate for particles under illumination compared to under dark heating, possibly implying a crucial role of localized heat gradients at the particle surface.
Finally, the coating thickness was identified as an essential parameter determining the photothermal conversion efficiency and the reaction acceleration.
We present the PINE (Plasma density in the Inner magnetosphere Neural network‐based Empirical) model ‐ a new empirical model for reconstructing the global dynamics of the cold plasma density distribution based only on solar wind data and geomagnetic indices. Utilizing the density database obtained using the NURD (Neural‐network‐based Upper hybrid Resonance Determination) algorithm for the period of 1 October 2012 to 1 July 2016, in conjunction with solar wind data and geomagnetic indices, we develop a neural network model that is capable of globally reconstructing the dynamics of the cold plasma density distribution for 2≤L≤6 and all local times. We validate and test the model by measuring its performance on independent data sets withheld from the training set and by comparing the model‐predicted global evolution with global images of He+ distribution in the Earth's plasmasphere from the IMAGE Extreme UltraViolet (EUV) instrument. We identify the parameters that best quantify the plasmasphere dynamics by training and comparing multiple neural networks with different combinations of input parameters (geomagnetic indices, solar wind data, and different durations of their time history). The optimal model is based on the 96 h time history of Kp, AE, SYM‐H, and F10.7 indices. The model successfully reproduces erosion of the plasmasphere on the nightside and plume formation and evolution. We demonstrate results of both local and global plasma density reconstruction. This study illustrates how global dynamics can be reconstructed from local in situ observations by using machine learning techniques.
We present the Neural-network-based Upper hybrid Resonance Determination (NURD) algorithm for automatic inference of the electron number density from plasma wave measurements made on board NASA's Van Allen Probes mission. A feedforward neural network is developed to determine the upper hybrid resonance frequency, fuhr, from electric field measurements, which is then used to calculate the electron number density. In previous missions, the plasma resonance bands were manually identified, and there have been few attempts to do robust, routine automated detections. We describe the design and implementation of the algorithm and perform an initial analysis of the resulting electron number density distribution obtained by applying NURD to 2.5 years of data collected with the Electric and Magnetic Field Instrument Suite and Integrated Science (EMFISIS) instrumentation suite of the Van Allen Probes mission. Densities obtained by NURD are compared to those obtained by another recently developed automated technique and also to an existing empirical plasmasphere and trough density model.
The Kp index is a measure of the midlatitude global geomagnetic activity and represents short-term magnetic variations driven by solar wind plasma and interplanetary magnetic field. The Kp index is one of the most widely used indicators for space weather alerts and serves as input to various models, such as for the thermosphere and the radiation belts. It is therefore crucial to predict the Kp index accurately. Previous work in this area has mostly employed artificial neural networks to nowcast Kp, based their inferences on the recent history of Kp and on solar wind measurements at L1. In this study, we systematically test how different machine learning techniques perform on the task of nowcasting and forecasting Kp for prediction horizons of up to 12 hr. Additionally, we investigate different methods of machine learning and information theory for selecting the optimal inputs to a predictive model. We illustrate how these methods can be applied to select the most important inputs to a predictive model of Kp and to significantly reduce input dimensionality. We compare our best performing models based on a reduced set of optimal inputs with the existing models of Kp, using different test intervals, and show how this selection can affect model performance.
Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization. Herein, we discover that during polymerization hydrogen sulfide evolves from the hydrolysis of carbonyl sulfide, which is the byproduct of ring-opening reaction, and reacts with NNTA to produce cyclic oligopeptoids. The capture of N-ethylethanethioic acid as an intermediate product confirms the reaction mechanism together with density functional theory quantum computational results. By bubbling the polymerization solution with argon, the side reaction can be suppressed to allow the synthesis of polysarcosine with high molar mass (M-n = 11,200 g/mol, D = 1.25) even in the presence of similar to 10,000 ppm of water.
We show that "stochastic bursting" is observed in a ring of unidirectional delay-coupled noisy excitable systems, thanks to the combinational action of time-delayed coupling and noise. Under the approximation of timescale separation, i.e., when the time delays in each connection are much larger than the characteristic duration of the spikes, the observed rather coherent spike pattern can be described by an idealized coupled point processwith a leader-follower relationship. We derive analytically the statistics of the spikes in each unit, the pairwise correlations between any two units, and the spectrum of the total output from the network. Theory is in good agreement with the simulations with a network of theta-neurons. Published under license by AIP Publishing.
We show that a combined action of noise and delayed feedback on an excitable theta-neuron leads to rather coherent stochastic bursting. An idealized point process, valid if the characteristic timescales in the problem are well separated, is used to describe statistical properties such as the power spectral density and the interspike interval distribution. We show how the main parameters of the point process, the spontaneous excitation rate, and the probability to induce a spike during the delay action can be calculated from the solutions of a stationary and a forced Fokker-Planck equation.
We investigate the transition from incoherence to global collective motion in a three-dimensional swarming model of agents with helical trajectories, subject to noise and global coupling. Without noise this model was recently proposed as a generalization of the Kuramoto model and it was found that alignment of the velocities occurs discontinuously for arbitrarily small attractive coupling. Adding noise to the system resolves this singular limit and leads to a continuous transition, either to a directed collective motion or to center-of-mass rotations.
OBJECTIVE: Higher plasma vitamin C levels are associated with lower type 2 diabetes risk, but whether this association is causal is uncertain. To investigate this, we studied the association of genetically predicted plasma vitamin C with type 2 diabetes.
RESEARCH DESIGN AND METHODS: We conducted genome-wide association studies of plasma vitamin C among 52,018 individuals of European ancestry to discover novel genetic variants. We performed Mendelian randomization analyses to estimate the association of genetically predicted differences in plasma vitamin C with type 2 diabetes in up to 80,983 case participants and 842,909 noncase participants. We compared this estimate with the observational association between plasma vitamin C and incident type 2 diabetes, including 8,133 case participants and 11,073 noncase participants.
RESULTS: We identified 11 genomic regions associated with plasma vitamin C (P < 5 x 10(-8)), with the strongest signal at SLC23A1, and 10 novel genetic loci including SLC23A3, CHPT1, BCAS3, SNRPF, RER1, MAF, GSTA5, RGS14, AKT1, and FADS1. Plasma vitamin C was inversely associated with type 2 diabetes (hazard ratio per SD 0.88; 95% CI 0.82, 0.94), but there was no association between genetically predicted plasma vitamin C (excluding FADS1 variant due to its apparent pleiotropic effect) and type 2 diabetes (1.03; 95% CI 0.96, 1.10).
CONCLUSIONS: These findings indicate discordance between biochemically measured and genetically predicted plasma vitamin C levels in the association with type 2 diabetes among European populations. The null Mendelian randomization findings provide no strong evidence to suggest the use of vitamin C supplementation for type 2 diabetes prevention.
This article offers a reconstruction of the vegetation and climate of the south-western Siberian Baraba forest-steppe area during the last ca. 8000 years. The analysis of palynological data from the sediment core of Lake Bolshie Toroki using quantitative methods has made it possible to reconstruct changes of the dominant types of vegetation and mean July air temperatures. Coniferous forests grew in the vicinity of the lake, and mean July air temperatures were similar to present-day ones between 7.9 and 7.0 kyr BP. The warmest and driest climate occurred at 7.0-5.0 kyr BP. At that time, the region had open steppe landscapes; birch groves began to spread. A cooling trend is seen after 5.5 kyr BP, when forest-steppe began to emerge. Steppe communities started to dominate again after 1.5 kyr BP. Mean July air temperatures lower than now are reconstructed for the period of 1.9-1 kyr BP, and then the temperatures became similar to present-day ones. Comparing the archaeological data on the types of economy of the population which inhabited the Baraba forest-steppe with the data on changes in the natural environment revealed a connection between the gradual transition from hunting and fishing to livestock breeding and the development of forest-steppe landscapes with a decrease in the area covered by forests. The development of the forest-steppe as an ecotonic landscape starting around 5 kyr BP might have contributed to the coexistence of several archaeological cultures with different types of economy on the same territory. (C) 2017 Elsevier Ltd. All rights reserved.
We study the properties of classical and quantum strongly nonlinear chains by means of extensive numerical simulations. Due to strong nonlinearity, the classical dynamics of such chains remains chaotic at arbitrarily low energies. We show that the collective excitations of classical chains are described by sound waves whose decay rate scales algebraically with the wave number with a generic exponent value. The properties of the quantum chains are studied by the quantum Monte Carlo method and it is found that the low-energy excitations are well described by effective phonon modes with the sound velocity dependent on an effective Planck constant. Our results show that at low energies the quantum effects lead to a suppression of chaos and drive the system to a quasi-integrable regime of effective phonon modes.
Melanoma represents a prime example demonstrating the success of targeted therapy in cancer. Nevertheless, it remained a deadly disease until now, and the identification of new, independent strategies as well as the understanding of their molecular mechanisms may help to finally overcome the high mortality. Both indirubins and TNF-related apoptosis-inducing ligand (TRAIL) represent promising candidates. Here, the indirubin derivative DKP-073 is shown to trigger apoptosis in melanoma cells, which is enhanced by the combination with TRAIL and is accompanied by complete loss of cell viability. Addressing the signaling cascade, characteristic molecular steps were identified as caspase-3 activation, downregulation of XIAP, upregulation of p53 and TRAIL receptor 2, loss of mitochondrial membrane potential, and STAT-3 dephosphorylation. The decisive step, however, turned out to be the early production of ROS already at 1 h. This was proven by antioxidant pretreatment, which completely abolished apoptosis induction and loss of cell viability as well as abrogated all signaling effects listed above. Thus, ROS appeared as upstream of all proapoptotic signaling. The data indicate a dominant role of ROS in apoptosis regulation, and the new pathway may expose a possible Achilles heel of melanoma.
Thick poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) [P(S-b-MDEGA-b-S)] films (thickness 5 mu m) are prepared from different solvents on flexible substrates by solution casting and investigated with small-angle X-ray scattering. As the solvents are either PS- or PMDEGA-selective, micelles with different core-shell micellar structures are formed. In PMDEGA-selective solvents, the PS block is the core and PMDEGA is the shell, whereas in PS-selective solvents, the order is reversed. After exposing the films to liquid D2O, the micellar structure inside the films prepared from PMDEGA-selective solvents remains unchanged and only the PMDEGA (shell part) swells. On the contrary, in the films prepared from PS-selective solvents, the micelles revert the core and the shell. This reversal causes more entanglements of the PMDEGA chains between the micelles. Moreover, the thermal collapse transition of the PMDEGA block in liquid D2O is significantly broadened. Irrespective of the solvent used for film preparation, the swollen PMDEGA shell does not show a prominent shrinkage when passing the phase transition, and the transition process occurs via compaction. The collapsed micelles have a tendency to densely pack above the transition temperature.
The switching kinetics of thin thermo-responsive hydrogel films of poly(monomethoxy-diethyleneglycol-acrylate) (PMDEGA) are investigated. Homogeneous and smooth PMDEGA films with a thickness of 35.9 nm are prepared on silicon substrates by spin coating. As probed with white light interferometry, PMDEGA films with a thickness of 35.9 nm exhibit a phase transition temperature of the lower critical solution temperature (LCST) type of 40 degrees C. In situ neutron reflectivity is performed to investigate the thermo-responsive behavior of these PMDEGA hydrogel films in response to a sudden thermal stimulus in deuterated water vapor atmosphere. The collapse transition proceeds in a complex way which can be seen as three steps. The first step is the shrinkage of the initially swollen film by a release of water. In the second step the thickness remains constant with water molecules embedded in the film. In the third step, perhaps due to a conformational rearrangement of the collapsed PMDEGA chains, water is reabsorbed from the vapor atmosphere, thereby giving rise to a relaxation process. Both the shrinkage and relaxation processes can be described by a simple model of hydrogel deswelling.
The isothermal vacuum-induced dehydration of thin films made of poly(methoxy diethylene glycol acrylate) (PMDEGA), which were swollen under ambient conditions, is studied. The dehydration behavior of the homopolymer film as well as of a nanostructured film of the amphiphilic triblock copolymer polystyrene-block-poly(methoxy diethylene glycol acrylate)-block-polystyrene, abbreviated as PS-b-PMDEGA-b-PS, are probed, and compared to the thermally induced dehydration behavior of such thin thermo-responsive films when they pass through their LCST-type coil-to globule collapse transition. The dehydration kinetics is followed by in-situ neutron reflectivity measurements. Contrast results from the use of deuterated water. Water content and film thickness are significantly reduced during the process, which can be explained by Schott second order kinetics theory for both films. The water content of the dehydrated equilibrium state from this model is very close to the residual water content obtained from the final static measurements, indicating that residual water still remains in the film even after prolonged exposure to the vacuum. In the PS-b-PMDEGA-b-PS film that shows micro-phase separation, the hydrophobic PS domains modify the dehydration process by hindering the water removal, and thus retarding dehydration by about 30%. Whereas residual water remains tightly bound in the PMDEGA domains, water is completely removed from the PS domains of the block copolymer film. (C) 2017 Elsevier Ltd. All rights reserved.
The rehydration of thermoresponsive polystyrene-block-poly(methoxy diethylene glycol acrylate)-block-polystyrene (PS-b-PMDEGA-b-PS) films forming a lamellar microphase-separated structure is investigated by in situ neutron reflectivity in a D2O vapor atmosphere. The rehydration of collapsed PS-b-PMDEGA-b-PS films is realized by a temperature change from 45 to 23 degrees C and comprises (1) condensation and absorption of D2O, (2) evaporation of D2O, and (3) reswelling of the film due to internal rearrangement. The hydrophobic PS layers hinder the absorption of condensed D2O, and a redistribution of embedded D2O between the hydrophobic PS layers and the hydrophilic PMDEGA layers is observed. In contrast, the rehydration of semiswollen PS-b-PMDEGA-b-PS films (temperature change from 35 to 23 degrees C) shows two prominent differences: A thicker D2O layer condenses on the surface, causing a more enhanced evaporation of D2O. The rehydrated films differ in film thickness and volume fraction of D2O, which is due to the different thermal protocols, although the final temperature is identical.
The rehydration of thermoresponsive poly(monomethoxydiethylene glycol acrylate) (PMDEGA) films exhibiting a lower critical solution temperature (LCST) type demixing phase transition in aqueous environments, induced by a decrease in temperature, is investigated in situ with real-time neutron reflectivity. Two different starting conditions (collapsed versus partially swollen chain conformation) are compared. In one experiment, the temperature is reduced from above the demixing temperature to well below the demixing temperature. In a second experiment, the starting temperature is below the demixing temperature, but within the transition regime, and reduced to the same final temperature. In both cases, the observed rehydration process can be divided into three stages: first condensation of water from the surrounding atmosphere, then absorption of water by the PMDEGA film and evaporation of excess water, and finally, rearrangement of the PMDEGA chains. The final rehydrated film is thicker and contains more absorbed water as compared with the initially swollen film at the same temperature well below the demixing temperature.
Thin thermoresponsive films of the triblock copolymer polystyrene-block-poly(methoxydiethylene glycol acrylate)-block-polystyrene (P(S-b-MDEGA-b-S)) are investigated on silicon substrates. By spin coating, homogeneous and smooth films are prepared for a range of film thicknesses from 6 to 82 nm. Films are stable with respect to dewetting as investigated with optical microscopy and atomic force microscopy. P(S-b-MDEGA-b-S) films with a thickness of 39 nm exhibit a phase transition of the lower critical solution temperature (LCST) type at 36.5 degrees C. The swelling and the thermoresponsive behavior of the films with respect to a sudden thermal stimulus are probed with in-situ neutron reflectivity. In undersaturated water vapor swelling proceeds without thickness increase. The thermoresponse proceeds in three steps: First, the film rejects water as the temperature is above LCST. Next, it stays constant for 600 s, before the collapsed film takes up water again. With ATR-FTIR measurements, changes of bound water in the film caused by different thermal stimuli are studied. Hydrogen bonds only form between C=O and water in the swollen film. Above the LCST most hydrogen bonds with water are broken, but some amount of bound water remains inside the film in agreement with the neutron reflectivity data. Grazing-incidence small-angle X-ray scattering (GISAXS) shows that the inner lateral structure is not significantly influenced by the different thermal stimuli.
The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)(3)) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)(3) films show a transition temperature (TT) at 33 degrees C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)(3) films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)(3). However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)(3) films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)(3) films depends on the final temperature. It decreases from (9.7 +/- 0.3)% to (7.0 +/- 0.3)% or (6.0 +/- 0.3)% when the final temperatures are set to 35 degrees C, 45 degrees C and 50 degrees C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.
The thermal behavior of poly(methoxydiethylenglycol acrylate) (PMDEGA) is studied in thin hydrogel films on solid supports and is compared with the behavior in aqueous solution. The PMDEGA hydrogel film thickness is varied from 2 to 422 nm. Initially, these films are homogenous, as measured with optical microscopy, atomic force microscopy, X-ray reflectivity, and grazing-incidence small-angle X-ray scattering (GISAXS). However, they tend to de-wet when stored under ambient conditions. Along the surface normal, no long-ranged correlations between substrate and film surface are detected with GISAXS, due to the high mobility of the polymer at room temperature. The swelling of the hydrogel films as a function of the water vapor pressure and the temperature are probed for saturated water vapor pressures between 2,380 and 3,170 Pa. While the swelling capability is found to increase with water vapor pressure, swelling in dependence on the temperature revealed a collapse phase transition of a lower critical solution temperature type. The transition temperature decreases from 40.6 A degrees C to 36.6 A degrees C with increasing film thickness, but is independent of the thickness for very thin films below a thickness of 40 nm. The observed transition temperature range compares well with the cloud points observed in dilute (0.1 wt.%) and semi-dilute (5 wt.%) solution which decrease from 45 A degrees C to 39 A degrees C with increasing concentration.
Organic photovoltaics based on non-fullerene acceptors (NFAs) show record efficiency of 16 to 17% and increased photovoltage owing to the low driving force for interfacial charge-transfer. However, the low driving force potentially slows down charge generation, leading to a tradeoff between voltage and current. Here, we disentangle the intrinsic charge-transfer rates from morphology-dependent exciton diffusion for a series of polymer:NFA systems. Moreover, we establish the influence of the interfacial energetics on the electron and hole transfer rates separately. We demonstrate that charge-transfer timescales remain at a few hundred femtoseconds even at near-zero driving force, which is consistent with the rates predicted by Marcus theory in the normal region, at moderate electronic coupling and at low re-organization energy. Thus, in the design of highly efficient devices, the energy offset at the donor:acceptor interface can be minimized without jeopardizing the charge-transfer rate and without concerns about a current-voltage tradeoff.
This paper assesses the seasonality of the urban heat island (UHI) effect in the Greater London area (United Kingdom). Combining satellite-based observations and urban boundary layer climate modeling with the UrbClim model, the authors are able to address the seasonality of UHI intensity, on the basis of both land surface temperature (LST) and 2-m air temperature, for four individual times of the day (0130, 1030, 1330, and 2230 local time) and the daily means derived from them. An objective of this paper is to investigate whether the UHI intensities that are based on both quantities exhibit a similar hysteresis-like trajectory that is observed for LST when plotting the UHI intensity against the background temperature. The results show that the UrbClim model can satisfactorily reproduce both the observed urban rural LSTs and 2-m air temperatures as well as their differences and the hysteresis in the surface UHI. The hysteresis-like seasonality is largely absent in both the observed and modeled 2-m air temperatures, however. A sensitivity simulation of the UHI intensity to incoming solar radiation suggests that the hysteresis of the LST can mainly be attributed to the seasonal variation in incoming solar radiation.
We perform a systematic study of all cities in Europe to assess the Urban Heat Island (UHI) intensity by means of remotely sensed land surface temperature data. Defining cities as spatial clusters of urban land cover, we investigate the relationships of the UHI intensity, with the cluster size and the temperature of the surroundings. Our results show that in Europe, the UHI intensity in summer has a strong correlation with the cluster size, which can be well fitted by an empirical sigmoid model. Furthermore, we find a novel seasonality of the UHI intensity for individual clusters in the form of hysteresis-like curves. We characterize the shape and identify apparent regional patterns.
Urban climate is determined by a variety of factors, whose knowledge can help to attenuate heat stress in the context of ongoing urbanization and climate change. We study the influence of city size and urban form on the Urban Heat Island (UHI) phenomenon in Europe and find a complex interplay between UHI intensity and city size, fractality, and anisometry. Due to correlations among these urban factors, interactions in the multi-linear regression need to be taken into account. We find that among the largest 5,000 cities, the UHI intensity increases with the logarithm of the city size and with the fractal dimension, but decreases with the logarithm of the anisometry. Typically, the size has the strongest influence, followed by the compactness, and the smallest is the influence of the degree to which the cities stretch. Accordingly, from the point of view of UHI alleviation, small, disperse, and stretched cities are preferable. However, such recommendations need to be balanced against e.g. positive agglomeration effects of large cities. Therefore, trade-offs must be made regarding local and global aims.
Noise-sustained and controlled synchronization of stirred excitable media by external forcing
(2005)
Most of the previous studies on constructive effects of noise in spatially extended systems have focused on static media, e.g., of the reaction diffusion type. Because many active chemical or biological processes occur in a fluid environment with mixing, we investigate here the interplay among noise, excitability, mixing and external forcing in excitable media advected by a chaotic flow, in a two-dimensional FitzHugh-Nagumo model described by a set of reaction- advection-diffusion equations. In the absence of external forcing, noise may generate sustained coherent oscillations of the media in a range of noise intensities and stirring rates. We find that these noise-sustained oscillations can be synchronized by external periodic signals much smaller than the threshold. Analysis of the locking regions in the parameter space of the signal period, stirring rate and noise intensity reveals that the mechanism underlying the synchronization behaviour is a matching between the time scales of the forcing signal and the noise-sustained oscillations. The results demonstrate that, in the presence of a suitable level of noise, the stirred excitable media act as self-sustained oscillatory systems and become much easier to be entrained by weak external forcing. Our results may be verified in experiments and are useful to understand the synchronization of population dynamics of oceanic ecological systems by annual cycles
We investigate noise-controlled resonant response of active media to weak periodic forcing, both in excitable and oscillatory regimes. In the excitable regime, we find that noise-induced irregular wave structures can be reorganized into frequency-locked resonant patterns by weak signals with suitable frequencies. The resonance occurs due to a matching condition between the signal frequency and the noise-induced inherent time scale of the media. m:1 resonant regions similar to the Arnold tongues in frequency locking of self-sustained oscillatory media are observed. In the self-sustained oscillatory regime, noise also controls the oscillation frequency and reshapes significantly the Arnold tongues. The combination of noise and weak signal thus could provide an efficient tool to manipulate active extended systems in experiments
Dynamical organization of connection weights is studied in scale-free networks of chaotic oscillators, where the coupling strength of a node from its neighbors develops adaptively according to the local synchronization property between the node and its neighbors. We find that when complete synchronization is achieved, the coupling strength becomes weighted and correlated with the topology due to a hierarchical transition to synchronization in heterogeneous networks. Importantly, such an adaptive process enhances significantly the synchronizability of the networks, which could have meaningful implications in the manipulation of dynamical networks
We study synchronization behavior in networks of coupled chaotic oscillators with heterogeneous connection degrees. Our focus is on regimes away from the complete synchronization state, when the coupling is not strong enough, when the oscillators are under the influence of noise or when the oscillators are nonidentical. We have found a hierarchical organization of the synchronization behavior with respect to the collective dynamics of the network. Oscillators with more connections (hubs) are synchronized more closely by the collective dynamics and constitute the dynamical core of the network. The numerical observation of this hierarchical synchronization is supported with an analysis based on a mean field approximation and the master stability function. (C) 2006 American Institute of Physics
Realistic networks display not only a complex topological structure, but also a heterogeneous distribution of weights in the connection strengths. Here we study synchronization in weighted complex networks and show that the synchronizability of random networks with a large minimum degree is determined by two leading parameters: the mean degree and the heterogeneity of the distribution of node's intensity, where the intensity of a node, defined as the total strength of input connections, is a natural combination of topology and weights. Our results provide a possibility for the control of synchronization in complex networks by the manipulation of a few parameters
How do diverse dynamical patterns arise from the topology of complex networks? We study synchronization dynamics in the cortical brain network of the cat, which displays a hierarchically clustered organization, by modeling each node (cortical area) with a subnetwork of interacting excitable neurons. We find that in the biologically plausible regime the dynamics exhibits a hierarchical modular organization, in particular, revealing functional clusters coinciding with the anatomical communities at different scales. Our results provide insights into the relationship between network topology and functional organization of complex brain networks.
How We Found Our IMU
(2020)
Inertial measurement units (IMUs) are commonly used for localization or movement tracking in pervasive healthcare-related studies, and gait analysis is one of the most often studied topics using IMUs. The increasing variety of commercially available IMU devices offers convenience by combining the sensor modalities and simplifies the data collection procedures. However, selecting the most suitable IMU device for a certain use case is increasingly challenging. In this study, guidelines for IMU selection are proposed. In particular, seven IMUs were compared in terms of their specifications, data collection procedures, and raw data quality. Data collected from the IMUs were then analyzed by a gait analysis algorithm. The difference in accuracy of the calculated gait parameters between the IMUs could be used to retrace the issues in raw data, such as acceleration range or sensor calibration. Based on our algorithm, we were able to identify the best-suited IMUs for our needs. This study provides an overview of how to select the IMUs based on the area of study with concrete examples, and gives insights into the features of seven commercial IMUs using real data.
Tailoring cell–surface interactions is important for the of design medical implants as well as regenerative medicine and tissue engineering materials. Here the single parameter system is transcended via translating hard nanotopology into soft polymeric hydrogel structures via hydrogel imprinting lithography. The response of these cells to the nanotopology of the same dimensions but with different mechanical properties displays unexpected behavior between “hard” tissue cells and “soft” tissue cells.
The Indus Molasse records orogenic sedimentation associated with uplift and erosion of the southern margin of Asia in the course of ongoing India-Eurasia collision. Detailed field investigation clarifies the nature and extent of the depositional contact between this molasse and the underlying basement units. We report the first dataset on detrital zircon U-Pb ages, Hf isotopes and apatite U-Pb ages for the autochthonous molasse in the Indus Suture Zone. A latest Oligocene depositional age is proposed on the basis of the youngest detrital zircon U-Pb age peak and is consistent with published biostratigraphic data. Multiple provenance indicators suggest exclusively northerly derivation with no input from India in the lowermost parts of the section. The results provide constraints on the uplift and erosion history of the Ladakh Range following the initial India-Asia collision.
The Puna Plateau, adjacent Eastern Cordillera and the Sierras Pampeanas of the central Andes are largely characterized by thick-skinned, basement-involved deformation. The Puna Plateau hosts similar to N-S trending bedrock ranges bounded by deep-seated reverse faults and sedimentary basins. We contribute to the understanding of thick-skinned dynamics in the Puna Plateau by constraining regional kinematics of the poorly understood southern Puna Plateau through a multidisciplinary approach. On the southeastern plateau, sandstone modal composition and detrital zircon U-Pb and apatite fission-track data from Cenozoic strata indicate basin accumulation during the late Eocene to early Oligocene (similar to 38-28 Ma). Provenance analysis reveals the existence of a regional-scale basin covering the southern Puna Plateau during late Eocene to early Oligocene time (similar to 38-28 Ma) that was sourced from both the western plateau and the eastern plateau margin and had a depocenter located to the west. Petrographic and detrital zircon U-Pb data reveal erosion of proximal western and eastern sources after 12 Ma, in mid-late Miocene time. This indicates that the regional basin was compartmentalized into small-scale depocenters by the growth of basement-cored ranges continuing into the late Miocene (similar to 12-8 Ma). We suggest that the Cenozoic history of the southern Puna Plateau records the formation of a regional basin that was possibly driven by lithospheric flexure during the late Eocene to early Oligocene, before the growth of distributed basement-cored ranges starting as early as the late Oligocene. (C) 2015 Elsevier B.V. All rights reserved.
Cardiovascular diseases are the main cause of death worldwide, and their prevalence is expected to rise in the coming years. Polymer-based artificial replacements have been widely used for the treatment of cardiovascular diseases. Coagulation and thrombus formation on the interfaces between the materials and the human physiological environment are key issues leading to the failure of the medical device in clinical implantation. The surface properties of the materials have a strong influence on the protein adsorption and can direct the blood cell adhesion behavior on the interfaces. Furthermore, implant-associated infections will be induced by bacterial adhesion and subsequent biofilm formation at the implantation site. Thus, it is important to improve the hemocompatibility of an implant by altering the surface properties. One of the effective strategies is surface passivation to achieve protein/cell repelling ability to reduce the risk of thrombosis.
This thesis consists of synthesis, functionalization, sterilization, and biological evaluation of bulk poly(glycerol glycidyl ether) (polyGGE), which is a highly crosslinked polyether-based polymer synthesized by cationic ring-opening polymerization. PolyGGE is hypothesized to be able to resist plasma protein adsorption and bacterial adhesion due to analogous chemical structure as polyethylene glycol and hyperbranched polyglycerol. Hydroxyl end groups of polyGGE provide possibilities to be functionalized with sulfates to mimic the anti-thrombogenic function of the endothelial glycocalyx.
PolyGGE was synthesized by polymerization of the commercially available monomer glycerol glycidyl ether, which was characterized as a mixture of mono-, di- and tri-glycidyl ether. Cationic ring opening-polymerization of this monomer was carried out by ultraviolet (UV) initiation of the photo-initiator diphenyliodonium hexafluorophosphate. With the increased UV curing time, more epoxides in the side chains of the monomers participated in chemical crosslinking, resulting in an increase of Young’s modulus, while the value of elongation at break of polyGGE first increased due to the propagation of the polymer chains then decreased with the increase of crosslinking density. Eventually, the chain propagation can be effectively terminated by potassium hydroxide aqueous solution. PolyGGE exhibited different tensile properties in hydrated conditions at body temperature compared to the values in the dry state at room temperature. Both Young’s modulus and values of elongation at break were remarkably reduced when tested in water at 37 °C, which was above the glass transition temperature of polyGGE. At physiological conditions, entanglements of the ployGGE networks unfolded and the free volume of networks were replaced by water molecules as softener, which increased the mobility of the polymer chains, resulting in a lower Young’s modulus.
Protein adsorption analysis was performed on polyGGE films with 30 min UV curing using an enzyme-linked immunosorbent assay. PolyGGE could effectively prevent the adsorption of human plasma fibrinogen, albumin, and fibronectin at the interface of human plasma and polyGGE films. The protein resistance of polyGGE was comparable to the negative controls: the hemocompatible polydimethylsiloxane (PDMS), showing its potential as a coating material for cardiovascular implants. Moreover, antimicrobial tests of bacterial activity using isothermal microcalorimetry and the microscopic image of direct bacteria culturing demonstrated that polyGGE could directly interfere biofilm formation and growth of both Gram-negative and antibiotic-resistant Gram-positive bacteria, indicating the potential application of polyGGE for combating the risk of hospital-acquired infections and preventing drug-resistant superbug spreading.
To investigate its cell compatibility, polyGGE films were extracted by different solvents (ethanol, chloroform, acetone) and cell culture medium. Indirect cytotoxicity tests showed extracted polyGGE films still had toxic effects on L929 fibroblast cells. High-performance liquid chromatography/electrospray ionization mass spectrometry revealed the occurrence of organochlorine-containing compounds released during the polymer-cell culture medium interaction. A constant level of those organochlorine-containing compounds was confirmed from GGE monomer by a specific peak of C-Cl stretching in infrared spectra of GGE. This is assumed to be the main reason causing the increased cell membrane permeability and decreased metabolic activity, leading to cell death. Attempts as changing solvents were made to remove toxic substances, however, the release of these small molecules seems to be sluggish. The densely crosslinked polyGGE networks can possibly contribute to the trapping of organochlorine-containing compounds. These results provide valuable information for exploring the potentially toxic substances, leaching from polyGGE networks, and propose a feasible strategy for minimizing the cytotoxicity via reducing their crosslinking density.
Sulfamic acid/ N-Methyl-2-pyrrolidone (NMP) were selected as the reagents for the sulfation of polyGGE surfaces. Fourier transform attenuated total reflection infrared spectroscopy (ATR-FT-IR) was used to monitor the functionalization kinetics and the results confirmed the successful sulfate grafting on the surface of polyGGE with the covalent bond -C-O-S-. X-ray photoelectron spectroscopy was used to determine the element composition on the surface and the cross-section of the functionalized polyGGE and sulfation within 15 min guarantees the sulfation only takes place on the surface while not occurring in the bulk of the polymer. The concentration of grafted sulfates increased with the increasing reaction time. The hydrophilicity of the surface of polyGGE was highly increased due to the increase of negatively charged end groups. Three sterilization techniques including autoclaving, gamma irradiation, and ethylene oxide (EtO) sterilization were used for polyGGE sulfates. Results from ATR-FT-IR and Toluidine Blue O quantitative assay demonstrated the total loss of the sulfates after autoclave sterilization, which was also confirmed by the increased water contact angle. Little influence on the concentration of sulfates was found for gamma-irradiated and autoclaving sterilized polyGGE sulfates. To investigate the thermal influence on polyGGE sulfates, one strategy was to use poly(hydroxyethyl acrylate) sulfates (PHEAS) for modeling. The thermogravimetric analysis profile of PHEAS demonstrated that sulfates are not thermally stable independent of the substrate materials and decomposition of sulfates occurs at around 100 °C. Although gamma irradiation also showed little negative effect on the sulfate content, the color change in the polyGGE sulfates indicates chemical or physical change might occur in the polymer. EtO sterilization was validated as the most suitable sterilization technique to maintain the chemical structure of polyGGE sulfates.
In conclusion, the conducted work proved that bulk polyGGE can be used as an antifouling coating material and shows its antimicrobial potential. Sulfates functionalization can be effectively realized using sulfamic acid/NMP. EtO sterilization is the most suitable sterilization technique for grafted sulfates. Besides, this thesis also offers a good strategy for the analysis of toxic leachable substances using suitable physicochemical characterization techniques. Future work will focus on minimizing/eliminating the release of toxic substances via reducing the crosslinking density. Another interesting aspect is to study whether grafted sulfates can meet the need for anti-thrombogenicity.
Sulfated biomolecules are known to influence numerous biological processes in all living organisms. Particularly, they contribute to prevent and inhibit the hypercoagulation condition. The failure of polymeric implants and blood contacting devices is often related to hypercoagulation and microbial contamination. Here, bioactive sulfated biomacromolecules are mimicked by sulfation of poly(glycerol glycidyl ether) (polyGGE) films. Autoclaving, gamma-ray irradiation and ethylene oxide (EtO) gas sterilization techniques were applied to functionalized materials. The sulfate group density and hydrophilicity of sulfated polymers were decreased while chain mobility and thermal degradation were enhanced post autoclaving when compared to those after EtO sterilization. These results suggest that a quality control after sterilization is mandatory to ensure the amount and functionality of functionalized groups are retained.
Nanomaterials play an important role in mimicking the biochemical and biophysical cues of the extracellular matrix in human mesenchymal stem cells (MSCs). Increasing studies have demonstrated the crucial impact of functional groups on MSCs, while limited research is available on how the functional group's density on nanoparticles regulates MSC behavior. Herein, the effects of dendritic polyglycerol (dPG)-conjugated gold nanostars (GNSs) with different densities of functional groups on the osteogenesis of MSCs are systematically investigated. dPG@GNS nanocomposites have good biocompatibility and the uptake by MSCs is in a functional group density-dependent manner. The osteogenic differentiation of MSCs is promoted by all dPG@GNS nanocomposites, in terms of alkaline phosphatase activity, calcium deposition, and expression of osteogenic protein and genes. Interestingly, the dPGOH@GNSs exhibit a slight upregulation in the expression of osteogenic markers, while the different charged densities of sulfate and amino groups show more efficacy in the promotion of osteogenesis. Meanwhile, the sulfated nanostars dPGS20@GNSs show the highest enhancement. Furthermore, various dPG@GNS nanocomposites exerted their effects by regulating the activation of Yes-associated protein (YAP) to affect osteogenic differentiation. These results indicate that dPG@GNS nanocomposites have functional group density-dependent influence on the osteogenesis of MSCs, which may provide a new insight into regulating stem cell fate.
Parafoveal semantic processing has recently been well documented in reading Chinese sentences, presumably because of language-specific features. However, because of a large variation of fixation landing positions on pretarget words, some preview words actually were located in foveal vision when readers' eyes landed close to the end of the pretarget words. None of the previous studies has completely ruled out a possibility that the semantic preview effects might mainly arise from these foveally processed preview words. This case, whether previously observed positive evidence for parafoveal semantic processing can still hold, has been called into question. Using linear mixed models, we demonstrate in this study that semantic preview benefit from word N+1 decreased if fixation on pretarget word N was close to the preview. We argue that parafoveal semantic processing is not a consequence of foveally processed preview words.
BackgroundDisruptions of reading processes due to text substitutions can measure how readers use lexical information. MethodsWith eye-movement recording, children and adults viewed sentences with either identical, orthographically similar, homophonic or unrelated substitutions of the first characters in target words. To the extent that readers rely on orthographic or phonological cues, substitutions that contain such cues should cause less disruption reading than do unrelated substitutions. ResultsOn pretarget words, there was a reliable reduction in gaze duration due to homophonic substitution only for children. On target words, we observed reliable recovery effects due to orthographic similarity for adults. On post-target words, adults had better orthographic-based and phonological-based recovery abilities than children. ConclusionsThe combination of eye movement recording and the error detection paradigm offers a novel implicit paradigm for studying reading development: during sentence reading, beginning readers of Chinese may rely on phonological mediation, while skilled readers have more direct access to semantics from orthography.
During sentence reading, low spatial frequency information afforded by spaces between words is the primary factor for eye guidance in spaced writing systems, whereas saccade generation for unspaced writing systems is less clear and under debate. In the present study, we investigated whether word-boundary information, provided by alternating colors (consistent or inconsistent with word-boundary information) influences saccade-target selection in Chinese. In Experiment 1, as compared to a baseline (i.e., uniform color) condition, word segmentation with alternating color shifted fixation location towards the center of words. In contrast, incorrect word segmentation shifted fixation location towards the beginning of words. In Experiment 2, we used a gaze-contingent paradigm to restrict the color manipulation only to the upcoming parafoveal words and replicated the results, including fixation location effects, as observed in Experiment 1. These results indicate that Chinese readers are capable of making use of parafoveal word-boundary knowledge for saccade generation, even if such information is unfamiliar to them. The present study provides novel support for the hypothesis that word segmentation is involved in the decision about where to fixate next during Chinese reading.
Barite concretions and bands are widely distributed in black shale-chert horizons in the Yurtus Formation of Lower Cambrian in Aksu area, northwestern Tarim Basin, NW China. They mainly consist of coarse-grained anhedral to euhedral barite crystals with minor dolomites and pyrites. Petrological features indicate these concretions grew from the porewater in unconsolidated sediments at shallow burial below sediment-water interface. The slight deviation of Sr-87/Sr-86 ratios (0.7083 to 0.7090) and significant elevated delta S-34 values (56.8-76.4 parts per thousand CDT) of barite samples with respect to those of the Early Cambrian seawater further support that barite deposits precipitated from the enclosed porewater in sediment column, which evolved from the penecontemporaneous seawater with weak interaction with the host fine-grained siliciclastic sediments and highly-depleted sulfate in response to prolonged strong bacterial sulfate reduction without necessary renewal. The abundant organic matters in the basal Yurtus Formation should have facilitated developing sulfate-depleted methanogenesis zone and sulfate-methane transition zone (SMTZ) slightly after deposition. Therefore, barite deposits in the Yurtus Formation most likely resulted from diagenetic barium cycling and persistently grew from the porewater in the static SMTZ with a low sedimentation rate in the Early Cambrian. In comparison with the distribution of sedimentary barites in geological records, we tentatively proposed that a transition in diagenetic barium cycling and associated mineralization may have occurred from the Precambrian to Cambrian periods; this scenario may be causally linked to the changes in marine ecology (the advent of mesozooplankton and associated faecal pellet) and geochemistry (the increase of seawater sulfate concentration). Thus, the occurrence of diagenetic barite deposits in the Yurtus Formation implies that diagenetic barium cycling and more effective scavenging of barium from CH4- and Ba-rich porewaters within sediments might have become an nonnegligible process in continental margin areas, at least, since the earliest Cambrian, which could have significantly impacted the marine barium cycling. (C) 2015 Elsevier B.V. All rights reserved.
Atmospheric interactions with land surface in the arctic based on regional climate model solutions
(2014)
The physiological functions of sphingolipids in animals have been intensively studied, while less attention has been paid to their roles in plants. Here, we reveal the involvement of sphingolipid delta8 desaturase (SlSLD) in the chilling resistance of tomato (Solanum lycopersicum cv. Micro-Tom). We used the virus-induced gene silencing (VIGS) approach to knock-down SlSLD expression in tomato leaves, and then evaluated chilling resistance. Changes in leaf cell structure under a chilling treatment were observed by transmission electron microscopy. In control plants, SlSLD was highly expressed in the fruit and leaves in response to a chilling treatment. The degree of chilling damage was greater in SlSLD-silenced plants than in control plants, indicating that SlSLD knock-down significantly reduced the chilling resistance of tomato. Compared with control plants, SlSLD-silenced plants showed higher relative electrolytic leakage and malondialdehyde content, and lower superoxide dismutase and peroxidase activities after a chilling treatment. Chilling severely damaged the chloroplasts in SlSLD-silenced plants, resulting in the disruption of chloroplast membranes, swelling of thylakoids, and reduced granal stacking. Together, these results show that SlSLD is crucial for chilling resistance in tomato.
Camellia sinensis synthesizes and emits a large variety of volatile phenylpropanoids and benzenoids (VPB). To investigate the enzymes involved in the formation of these VPB compounds, a new C. sinensis short-chain dehydrogenase/reductase (CsSDR) was isolated, cloned, sequenced, and functionally characterized. The complete open reading frame of CsSDR contains 996 nucleotides with a calculated protein molecular mass of 34.5 kDa. The CsSDR recombinant protein produced in Escherichia coli exhibited dehydrogenase-reductase activity towards several major VPB compounds in C. sinensis flowers with a strong preference for NADP/NADPH co-factors, and showed affinity for (R)/(S)-1-phenylethanol (1PE), phenylacetaldehyde, benzaldehyde, and benzyl alcohol, and no affinity for acetophenone (AP) and 2-phenylethanol. CsSDR showed the highest catalytic efficiency towards (R)/(S)-1PE. Furthermore, the transient expression analysis in Nicotiana benthamiana plants validated that CsSDR could convert 1PE to AP in plants. CsSDR transcript level was not significantly affected by floral development and some jasmonic acid-related environmental stress, and CsSDR transcript accumulation was detected in most floral tissues such as receptacle and anther, which were main storage locations of VPB compounds. Our results indicate that CsSDR is expressed in C. sinensis flowers and is likely to contribute to a number of floral VPB compounds including the 1PE derivative AP.
Mimicking non-verbal emotional expressions and empathy development in simulated consultations
(2018)
Objective: To explore the feasibility of applying an experimental design to study the relationship between non-verbal emotions and empathy development in simulated consultations.
Method: In video-recorded simulated consultations, twenty clinicians were randomly allocated to either an experimental group (instructed to mimic non-verbal emotions of a simulated patient, SP) or a control group (no such instruction). Baseline empathy scores were obtained before consultation, relational empathy was rated by SP after consultation. Multilevel logistic regression modelled the probability of mimicry occurrence, controlling for baseline empathy and clinical experience. ANCOVA compared group differences on relational empathy and consultation smoothness.
Results: Instructed mimicry lasted longer than spontaneous mimicry. Mimicry was marginally related to improved relational empathy. SP felt being treated more like a whole person during consultations with spontaneous mimicry. Clinicians who displayed spontaneous mimicry felt consultations went more smoothly.
Conclusion: The experimental approach improved our understanding of how non-verbal emotional mimicry contributed to relational empathy development during consultations. Further work should ascertain the potential of instructed mimicry to enhance empathy development.
Practice implications: Understanding how non-verbal emotional mimicry impacts on patients’ perceived clinician empathy during consultations may inform training and intervention programme development.
This study investigated how touching and being touched by a humanoid robot affects human physiology, impressions of the interaction, and attitudes towards humanoid robots. 21 healthy adult participants completed a 3 (touch style: touching, being touched, pointing) x 2 (body part: hand vs buttock) within-subject design using a Pepper robot. Skin conductance response (SCR) was measured during each interaction. Perceived impressions of the interaction (i.e., friendliness, comfort, arousal) were measured per questionnaire after each interaction. Participants' demographics and their attitude towards robots were also considered. We found shorter SCR rise times in the being touched compared to the touching condition, possibly reflecting psychological alertness to the unpredictability of robot-initiated contacts. The hand condition had shorter rise times than the buttock condition. Most participants evaluated the hand condition as most friendly and comfortable and the robot-initiated interactions as most arousing. Interacting with Pepper improved attitudes towards robots. Our findings require future studies with larger samples and improved procedures. They have implications for robot design in all domains involving tactile interactions, such as caring and intimacy.
Earthquake site responses or site effects are the modifications of surface geology to seismic waves. How well can we predict the site effects (average over many earthquakes) at individual sites so far? To address this question, we tested and compared the effectiveness of different estimation techniques in predicting the outcrop Fourier site responses separated using the general inversion technique (GIT) from recordings. Techniques being evaluated are (a) the empirical correction to the horizontal-to-vertical spectral ratio of earthquakes (c-HVSR), (b) one-dimensional ground response analysis (GRA), and (c) the square-root-impedance (SRI) method (also called the quarter-wavelength approach). Our results show that c-HVSR can capture significantly more site-specific features in site responses than both GRA and SRI in the aggregate, especially at relatively high frequencies. c-HVSR achieves a "good match" in spectral shape at similar to 80%-90% of 145 testing sites, whereas GRA and SRI fail at most sites. GRA and SRI results have a high level of parametric and/or modeling errors which can be constrained, to some extent, by collecting on-site recordings.
The within-site variability in site response is the randomness in site response at a given site from different earthquakes and is treated as aleatory variability in current seismic hazard/risk analyses.
In this study, we investigate the single-station variability in linear site response at K-NET and KiK-net stations in Japan using a large number of earthquake recordings.
We found that the standard deviation of the horizontal-to-vertical Fourier spectral ratio at individual sites, that is single-station horizontal-to-vertical spectral ratio (HVSR) sigma sigma(HV,s), approximates the within-site variability in site response quantified using surface-to-borehole spectral ratios (for oscillator frequencies higher than the site fundamental frequency) or empirical ground-motion models.
Based on this finding, we then utilize the single-station HVSR sigma as a convenient tool to study the site-response variability at 697 KiK-net and 1169 K-NET sites.
Our results show that at certain frequencies, stiff, rough and shallow sites, as well as small and local events tend to have a higher sigma(HV,s).
However, when being averaged over different sites, the single-station HVSR sigma, that is sigma(HV), increases gradually with decreasing frequency. In the frequency range of 0.25-25 Hz, sigma(HV) is centred at 0.23-0.43 in ln scales (a linear scale factor of 1.26-1.54) with one standard deviation of less than 0.1. sigma(HV) is quite stable across different tectonic regions, and we present a constant, as well as earthquake magnitude- and distance-dependent sigma(HV) models.
In the Next Generation Attenuation West2 (NGA-West2) project, a 3D subsurface structure model (Japan Seismic Hazard Information Station [J-SHIS]) was queried to establish depths to 1.0 and 2.5 km/s velocity isosurfaces for sites without depth measurement in Japan. In this article, we evaluate the depth parameters in the J-SHIS velocity model by comparing them with their corresponding site-specific depth measurements derived from selected KiK-net velocity profiles. The comparison indicates that the J-SHIS model underestimates site depths at shallow sites and overestimates depths at deep sites. Similar issues were also identified in the southern California basin model. Our results also show that these underestimations and over-estimations have a potentially significant impact on ground-motion prediction using NGA-West2 ground-motion models (GMMs). Site resonant period may be considered as an alternative to depth parameter in the site term of a GMM.
In this investigation, we examine the uncertainties using the horizontal-to-vertical spectral ratio (HVSR) technique on earthquake recordings to detect site resonant frequencies at 207 KiK-net sites. Our results show that the scenario dependence of response (pseudospectral acceleration) spectral ratio could bias the estimates of resonant frequencies for sites having multiple significant peaks with comparable amplitudes. Thus, the Fourier amplitude spectrum (FAS) should be preferred in computing HVSR. For more than 80% of the investigated sites, the first peak (in the frequency domain) on the average HVSR curve over multiple sites coincides with the highest peak. However, for sites with multiple peaks, the highest peak frequency (f(p)) is less susceptible to the selection criteria of significant peaks and the extent of smoothing to spectrum than the first peak frequency (f(0)). Meanwhile, in comparison to the surface-to-borehole spectral ratio, f(0) tends to underestimate the predominant frequency (at which the largest amplification occurs) more than f(p). In addition, in terms of characterizing linear site response, f(p) shows a better overall performance than f(0). Based on these findings, we thus recommend that seismic network operators provide f(p) on the average HVSRFAS curve as a priority, ideally together with the average HVSRFAS curve in site characterization.
This study aims to identify the best-performing site characterization proxy alternative and complementary to the conventional 30 m average shear-wave velocity V-S30, as well as the optimal combination of proxies in characterizing linear site response. Investigated proxies include T-0 (site fundamental period obtained from earthquake horizontal-to-vertical spectral ratios), V-Sz (measured average shear-wave velocities to depth z, z = 5, 10, 20 and 30 m), Z(0.8) and Z(1.0) (measured site depths to layers having shear-wave velocity 0.8 and 1.0 km/s, respectively), as well as Z(x-infer) (inferred site depths from a regional velocity model, x = 0.8 and 1.0, 1.5 and 2.5 km/s). To evaluate the performance of a site proxy or a combination, a total of 1840 surface-borehole recordings is selected from KiK-net database. Site amplifications are derived using surface-to-borehole response-, Fourier- and cross-spectral ratio techniques and then are compared across approaches. Next, the efficacies of 7 single-proxies and 11 proxy-pairs are quantified based on the site-to-site standard deviation of amplification residuals of observation about prediction using the proxy or the pair. Our results show that T-0 is the best-performing single-proxy among T-0, Z(0.8), Z(1.0) and V-Sz. Meanwhile, T-0 is also the best-performing proxy among T-0, Z(0.8), Z(1.0) and Z(x-infer) complementary to V-S30 in accounting for the residual amplification after V-S30-correction. Besides, T-0 alone can capture most of the site effects and should be utilized as the primary site indicator. Though (T-0, V-S30) is the best-performing proxy pair among (V-S30, T-0), (V-S30, Z(0.8)), (V-S30, Z(1.0)), (V-S30, Z(x-infer)) and (T-0, V-Sz), it is only slightly better than (T-0, V-S20). Considering both efficacy and engineering utility, the combination of T-0 (primary) and V-S20 (secondary) is recommended. Further study is needed to test the performances of various proxies on sites in deep sedimentary basins.
Evaluation of a novel application of earthquake HVSR in site-specific amplification estimation
(2020)
Ground response analyses (GRA) model the vertical propagations of SH waves through flat-layered media (1DSH) and are widely carried out to evaluate local site effects in practice. Horizontal-to-vertical spectral ratio (HVSR) technique is a cost-effective approach to extract certain site-specific information, e.g., site fundamental frequency (f(0)), but HVSR values cannot be directly used to approximate the levels of S-wave amplifications. Motivated by the work of Kawase et al. (2019), we propose a procedure to correct earthquake HVSR amplitudes for direct amplification estimations. The empirical correction compensates HVSR by generic vertical amplification spectra categorized by the vertical fundamental frequency (f(0v)) via kappa-means clustering. In this investigation, we evaluate the effectiveness of the corrected HVSR in approximating observed linear amplifications in comparison with 1DSH modellings. We select a total of 90 KiK-net (Kiban Kyoshin network) surface-downhole sites which are found to have no velocity contrasts below their boreholes and thus of which surface-to-borehole spectral ratios (SBSRs) can be taken as their empirical transfer functions (ETFs). 1DSH-based theoretical transfer functions (TTFs) are computed in the linear domain considering uncertainties in Vs profiles through randomizations. Five goodness-of-fit metrics are adopted to gauge the closeness between observed (ETF) and predicted (i.e., TTF and corrected HVSR) amplifications in both amplitude and spectral shape over frequencies from f(0) to 25 Hz. We find that the empirical correction to HVSR is highly effective and achieves a "good match" in both spectral shape and amplitude at the majority of the 90 KiK-net sites, as opposed to less than one-third for the 1DSH modelling. In addition, the empirical correction does not require a velocity model, which GRAs require, and thus has great potentials in seismic hazard assessments.
The all-female Amazon molly (Poecilia formosa) is the result of a hybridization of the Atlantic molly (P. mexicana) and the sailfin molly (P. latipinna) approximately 120,000 years ago. As a gynogenetic species, P. formosa needs to copulate with heterospecific males including males from one of its bisexual ancestral species. However, the sperm only triggers embryogenesis of the diploid eggs. The genetic information of the sperm donor typically will not contribute to the next generation of P. formosa. Hence, P. formosa possesses generally one allele from each of its ancestral species at any genetic locus. This raises the question whether both ancestral alleles are equally expressed in P. formosa. Allele-specific expression (ASE) has been previously assessed in various organisms, e.g., human and fish, and ASE was found to be important in the context of phenotypic variability and disease. In this study, we utilized Real-Time PCR techniques to estimate ASE of the androgen receptor alpha (arα) gene in several distinct tissues of Amazon mollies. We found an allelic bias favoring the maternal ancestor (P. mexicana) allele in ovarian tissue. This allelic bias was not observed in the gill or the brain tissue. Sequencing of the promoter regions of both alleles revealed an association between an Indel in a known CpG island and differential expression. Future studies may reveal whether our observed cis-regulatory divergence is caused by an ovary-specific trans-regulatory element, preferentially activating the allele of the maternal ancestor.
The all-female Amazon molly (Poecilia formosa) originated from a single hybridization of two bisexual ancestors, Atlantic molly (Poecilia mexicana) and sailfin molly (Poecilia latipinna). As a gynogenetic species, the Amazon molly needs to copulate with a heterospecific male, but the genetic information of the sperm-donor does not contribute to the next generation, as the sperm only acts as the trigger for the diploid eggs’ embryogenesis. Here, we study the sequence evolution and gene expression of the duplicated genes coding for androgen receptors (ars) and other pathway-related genes, i.e., the estrogen receptors (ers) and cytochrome P450, family19, subfamily A, aromatase genes (cyp19as), in the Amazon molly, in comparison to its bisexual ancestors. Mollies possess–as most other teleost fish—two copies of the ar, er, and cyp19a genes, i.e., arα/arβ, erα/erβ1, and cyp19a1 (also referred as cyp19a1a)/cyp19a2 (also referred to as cyp19a1b), respectively. Non-synonymous single nucleotide polymorphisms (SNPs) among the ancestral bisexual species were generally predicted not to alter protein function. Some derived substitutions in the P. mexicana and one in P. formosa are predicted to impact protein function. We also describe the gene expression pattern of the ars and pathway-related genes in various tissues (i.e., brain, gill, and ovary) and provide SNP markers for allele specific expression research. As a general tendency, the levels of gene expression were lowest in gill and highest in ovarian tissues, while expression levels in the brain were intermediate in most cases. Expression levels in P. formosa were conserved where expression did not differ between the two bisexual ancestors. In those cases where gene expression levels significantly differed between the bisexual species, P. formosa expression was always comparable to the higher expression level among the two ancestors. Interestingly, erβ1 was expressed neither in brain nor in gill in the analyzed three molly species, which implies a more important role of erα in the estradiol synthesis pathway in these tissues. Furthermore, our data suggest that interactions of steroid-signaling pathway genes differ across tissues, in particular the interactions of ars and cyp19as.
The all-female Amazon molly (Poecilia formosa) is the result of a hybridization of the Atlantic molly (P. mexicana) and the sailfin molly (P. latipinna) approximately 120,000 years ago. As a gynogenetic species, P. formosa needs to copulate with heterospecific males including males from one of its bisexual ancestral species. However, the sperm only triggers embryo genesis of the diploid eggs. The genetic information of the sperm donor typically will not contribute to the next generation of P. formosa. Hence, P. formosa possesses generally one allele from each of its ancestral species at any genetic locus. This raises the question whether both ancestral alleles are equally expressed in P. formosa. Allele-specific expression (ASE) has been previously assessed in various organisms, e.g., human and fish, and ASE was found to be important in the context of phenotypic variability and disease. In this study, we utilized Real-Time PCR techniques to estimate ASE of the androgen receptor alpha (ara) gene in several distinct tissues of Amazon mollies. We found an allelic bias favoring the maternal ancestor (P. mexicana) allele in ovarian tissue. This allelic bias was not observed in the gill or the brain tissue. Sequencing of the promoter regions of both alleles revealed an association between an Indel in a known CpG island and differential expression. Future studies may reveal whether our observed cis-regulatory divergence is caused by an ovary-specific trans-regulatory element, preferentially activating the allele of the maternal ancestor.
The all-female Amazon molly (Poecilia formosa) originated from a single hybridization of two bisexual ancestors, Atlantic molly (Poecilia mexicana) and sailfin molly (Poecilia latipinna). As a gynogenetic species, the Amazon molly needs to copulate with a heterospecific male, but the genetic information of the sperm-donor does not contribute to the next generation, as the sperm only acts as the trigger for the diploid eggs’ embryogenesis. Here, we study the sequence evolution and gene expression of the duplicated genes coding for androgen receptors (ars) and other pathway-related genes, i.e., the estrogen receptors (ers) and cytochrome P450, family19, subfamily A, aromatase genes (cyp19as), in the Amazon molly, in comparison to its bisexual ancestors. Mollies possess–as most other teleost fish—two copies of the ar, er, and cyp19a genes, i.e., arα/arβ, erα/erβ1, and cyp19a1 (also referred as cyp19a1a)/cyp19a2 (also referred to as cyp19a1b), respectively. Non-synonymous single nucleotide polymorphisms (SNPs) among the ancestral bisexual species were generally predicted not to alter protein function. Some derived substitutions in the P. mexicana and one in P. formosa are predicted to impact protein function. We also describe the gene expression pattern of the ars and pathway-related genes in various tissues (i.e., brain, gill, and ovary) and provide SNP markers for allele specific expression research. As a general tendency, the levels of gene expression were lowest in gill and highest in ovarian tissues, while expression levels in the brain were intermediate in most cases. Expression levels in P. formosa were conserved where expression did not differ between the two bisexual ancestors. In those cases where gene expression levels significantly differed between the bisexual species, P. formosa expression was always comparable to the higher expression level among the two ancestors. Interestingly, erβ1 was expressed neither in brain nor in gill in the analyzed three molly species, which implies a more important role of erα in the estradiol synthesis pathway in these tissues. Furthermore, our data suggest that interactions of steroid-signaling pathway genes differ across tissues, in particular the interactions of ars and cyp19as.
In this paper we report a rare and fortunate event of fast magnetosonic (MS, also called equatorial noise) waves modulated by compressional ultralow frequency (ULF) waves measured by Van Allen Probes. The characteristics of MS waves, ULF waves, proton distribution, and their potential correlations are analyzed. The results show that ULF waves can modulate the energetic ring proton distribution and in turn modulate the MS generation. Furthermore, the variation of MS intensities is attributed to not only ULF wave activities but also the variation of background parameters, for example, number density. The results confirm the opinion that MS waves are generated by proton ring distribution and propose a new modulation phenomenon.
Whistler mode exohiss are the structureless hiss waves observed outside the plasma pause with featured equatorward Poynting flux. An event of the amplification of exohiss as well as chorus waves was recorded by Van Allen Probes during the recovery phase of a weak geomagnetic storm. Amplitudes of both types of the waves showed a significant increase at the regions of electron density enhancements. It is found that the electrons resonant with exohiss and chorus showed moderate pitch angle anisotropies. The ratio of the number of electrons resonating with exohiss to total electron number presented in-phase correlation with density variations, which suggests that exohiss can be amplified due to electron density enhancement in terms of cyclotron instability. The calculation of linear growth rates further supports above conclusion. We suggest that exohiss waves have potential to become more significant due to the background plasma fluctuation.
New wave frequency and amplitude models for the nightside and dayside chorus waves are built based on measurements from the Electric and Magnetic Field Instrument Suite and Integrated Science (EMFISIS) instrument onboard the Van Allen Probes. The corresponding 3D diffusion coefficients are systematically obtained. Compared with previous commonly-used (typical) parameterizations, the new parameterizations result in differences in diffusion rates that depend on the energy and pitch angle. Furthermore, one-year 3D diffusive simulations are performed using the Versatile Electron Radiation Belt (VERB) code. Both typical and new wave parameterizations simulation results are in a good agreement with observations at 0.9 MeV. However, the new parameterizations for nightside chorus better reproduce the observed electron fluxes. These parameterizations will be incorporated into future modeling efforts.
A membrane of a dielectric elastomer coated with compliant electrodes may form wrinkles as the applied voltage is ramped up. We present a combination of experiment and theory to investigate the transition to wrinkles using a clamped membrane subject to a constant force and a voltage ramp. Two types of transitions are identified. In type-I transition, the voltage-stretch curve is N-shaped, and flat and wrinkled regions coexist in separate areas of the membrane. The type-I transition progresses by nucleation of small wrinkled regions, followed by the growth of the wrinkled regions at the expense of the flat regions, until the entire membrane is wrinkled. By contrast, in type-II transition, the voltage-stretch curve is monotonic, and the entire flat membrane becomes wrinkled with no nucleation barrier. The two types of transitions are analogous to the first and the second order phase transitions. While the type-I transition is accompanied by a jump in the vertical displacement, type-II transition is accompanied by a continuous change in the vertical displacement. Such transitions may enable applications in muscle-like actuation and energy harvesting, where large deformation and large energy of conversion are desired.
This paper theoretically analyzes a dielectric elastomer tube actuator (DETA). Subject to a voltage difference between the inner and outer surfaces, the actuator reduces in thickness and expands in length, so that the same voltage will induce an even higher electric field. This positive feedback may cause the actuator to thin down drastically, resulting in electrical breakdown. We obtain an analytical solution of the actuator undergoing finite deformation when the elastomer obeys the neo-Hookean model. The critical strain of actuation is calculated in terms of various parameters of design. We also discuss the effect of the strain-stiffening on electromechanical behavior of DETAs by using the model of freely joined links. (C) 2010 American Institute of Physics. [doi:10.1063/1.3490186]
The Kyoto Protocol’s Clean Development Mechanism (CDM) allows developed countries to meet part of their obligational emission reductions by carrying out emission reduction projects in developing countries. China imposed a price floor to the CDM carbon credits produced in China through its price review policy. Scholars have not agreed on the purpose of China’s price review policy. With a theoretical model and a coherent empirical study, the present study shows that the price floor imposed by China’s price review is more likely to protect those domestic project owners against price discrimination, rather than to distort the CDM market. Nevertheless, China’s price review has its own flaws. Although a regression study shows month of approval, types of projects and location of project can explain 55% of price floor designation, the operation of price review remains quite random and unpredictable in individual cases. This would bring extra bureaucratically uncertainty on its way to curb market uncertainty. Its function can be fulfilled by alternative policy tools with better economic efficiency and legal legitimacy, such as mandatory price disclosure and trading forum, which doesn’t have such drawback, but still be able to alleviate possible price discrimination in individual cases.
We consider networks of chaotic maps with different network topologies. In each case, they are coupled in such a way as to generate synchronized chaotic solutions. By using the methods of control of chaos we are controlling a single map into a predetermined trajectory. We analyze the reaction of the network to such a control. Specifically we show that a line of one-dimensional logistic maps that are unidirectionally coupled can be controlled from the first oscillator whereas a ring of diffusively coupled maps cannot be controlled for more than 5 maps. We show that rings with more elements can be controlled if every third map is controlled. The dependence of unidirectionally coupled maps on noise is studied. The noise level leads to a finite synchronization lengths for which maps can be controlled by a single location. A two-dimensional lattice is also studied. (C) 2005 American Institute of Physics
Mechanical behaviors of granite after thermal treatment under loading and unloading conditions
(2021)
Understanding the mechanical behaviors of granite after thermal treatment under loading and unloading conditions is of utmost relevance to deep geothermal energy recovery. In the present study, a series of loading and unloading triaxial compression tests (20, 40 and 60 MPa) on granite specimens after exposure to different temperatures (20, 200, 300, 400, 500 and 600 degrees C) was carried out to quantify the combined effects of thermal treatment and loading/unloading stress conditions on granite strength and deformation. Changes in the microstructure of granite exposed to high temperatures were revealed by optical microscopy. The experimental results indicate that both, thermal treatment and loading/unloading stress conditions, degrade the mechanical behaviors and further decrease the carrying capacity of granite. The gradual degradation of the mechanical characteristics of granite after thermal treatment is mainly associated with the evolution of thermal micro-cracks based on optical microscopy observations. The unloading stress state induces the extension of tension cracks parallel to the axial direction, and thus, the mechanical properties are degraded. Temperatures above 400 degrees C have a more significant influence on the mechanical characteristics of granite than the unloading treatment, whereby 400 degrees C can be treated as a threshold temperature for the delineation of significant deterioration. This study is expected to support feasibility and risk assessments by means of providing data for analytical calculations and numerical simulations on granite exposed to high temperatures during geothermal energy extraction.
Understanding the geologic evolution of Northern Tibetan Plateau with multiple thermochronometers
(2018)
The early onset of deformation following the India-Asia collision, Neogene expanse of uplift, and complex systems that comprise strike-slip faults, thrust faults, and intermontane basins characterize the Cenozoic tectonism of Northern Tibetan Plateau and raise two prominent questions in orogenic geodynamics: 1) What mechanism(s) control(s) the transfer of stress related to the India-Asia collision across the distance of >2000 km; and 2) Why the development of high topography was delayed in the Northern Tibetan Plateau and what does it reveal about how the internal forces and external boundary conditions evolved. To address these two questions, we reconstruct a holistic spatial-temporal deformation history of the Northern Tibetan Plateau by using a range of thermochronometers, with closure temperature spanning from 350 degrees C to-60-70 degrees C. This multi-thermochronometer study reveals three stages of faulting related cooling, in the early Cretaceous, in Paleocene-Eocene and in middle-late Miocene. We observe that Paleocene-Eocene deformation was spatially restricted and mostly occurred on reactivated Cretaceous structures, indicating a control of pre-existing weakness on early Cenozoic deformation. Extensive Neogene deformation contrasts with restricted Paleocene-Eocene deformation and relatively quiescent shortening during the Oligocene-early Miocene, which implies a change in the regional tectonics regime. Global plate reconstructions show that this tectonic reorganization is coeval with an increase in Pacific-Asia plate convergence rates. We argue that this change in regional tectonics is a result of increasing constrictive environment of the eastern plate boundary, which changed the behavior of the Altyn Tagh fault the boundary fault of Northern Tibetan Plateau, causing it to change from feeding slip into structures out of the plateau to feeding slip into structures at plateau margins.