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Background
To determine the general appearance of normal axillary lymph nodes (LNs) in real-time tissue sonoelastography and to explore the method′s potential value in the prediction of LN metastases.
Methods
Axillary LNs in healthy probands (n=165) and metastatic LNs in breast cancer patients (n=15) were examined with palpation, B-mode ultrasound, Doppler and sonoelastography (assessment of the elasticity of the cortex and the medulla). The elasticity distributions were compared and sensitivity (SE) and specificity (SP) were calculated. In an exploratory analysis, positive and negative predictive values (PPV, NPV) were calculated based upon the estimated prevalence of LN metastases in different risk groups.
Results
In the elastogram, the LN cortex was significantly harder than the medulla in both healthy (p=0.004) and metastatic LNs (p=0.005). Comparing healthy and metastatic LNs, there was no difference in the elasticity distribution of the medulla (p=0.281), but we found a significantly harder cortex in metastatic LNs (p=0.006). The SE of clinical examination, B-mode ultrasound, Doppler ultrasound and sonoelastography was revealed to be 13.3%, 40.0%, 14.3% and 60.0%, respectively, and SP was 88.4%, 96.8%, 95.6% and 79.6%, respectively. The highest SE was achieved by the disjunctive combination of B-mode and elastographic features (cortex >3mm in B-mode or blue cortex in the elastogram, SE=73.3%). The highest SP was achieved by the conjunctive combination of B-mode ultrasound and elastography (cortex >3mm in B-mode and blue cortex in the elastogram, SP=99.3%).
Conclusions
Sonoelastography is a feasible method to visualize the elasticity distribution of LNs. Moreover, sonoelastography is capable of detecting elasticity differences between the cortex and medulla, and between metastatic and healthy LNs. Therefore, sonoelastography yields additional information about axillary LN status and can improve the PPV, although this method is still experimental.
Background: To determine the general appearance of normal axillary lymph nodes (LNs) in real-time tissue sonoelastography and to explore the method's potential value in the prediction of LN metastases.
Methods: Axillary LNs in healthy probands (n=165) and metastatic LNs in breast cancer patients (n=15) were examined with palpation, B-mode ultrasound, Doppler and sonoelastography (assessment of the elasticity of the cortex and the medulla). The elasticity distributions were compared and sensitivity (SE) and specificity (SP) were calculated. In an exploratory analysis, positive and negative predictive values (PPV, NPV) were calculated based upon the estimated prevalence of LN metastases in different risk groups.
Results: In the elastogram, the LN cortex was significantly harder than the medulla in both healthy (p=0.004) and metastatic LNs (p=0.005). Comparing healthy and metastatic LNs, there was no difference in the elasticity distribution of the medulla (p=0.281), but we found a significantly harder cortex in metastatic LNs (p=0.006). The SE of clinical examination, B-mode ultrasound, Doppler ultrasound and sonoelastography was revealed to be 13.3%, 40.0%, 14.3% and 60.0%, respectively, and SP was 88.4%, 96.8%, 95.6% and 79.6%, respectively. The highest SE was achieved by the disjunctive combination of B-mode and elastographic features (cortex >3mm in B-mode or blue cortex in the elastogram, SE=73.3%). The highest SP was achieved by the conjunctive combination of B-mode ultrasound and elastography (cortex >3mm in B-mode and blue cortex in the elastogram, SP=99.3%).
Conclusions: Sonoelastography is a feasible method to visualize the elasticity distribution of LNs. Moreover, sonoelastography is capable of detecting elasticity differences between the cortex and medulla, and between metastatic and healthy LNs. Therefore, sonoelastography yields additional information about axillary LN status and can improve the PPV, although this method is still experimental.
Objectives-The purpose of this study was to determine the dependence of breast tissue elasticity on the menstrual cycle of healthy volunteers by means of real-time sonoelastography.
Methods-Twenty-two healthy volunteers (aged 18-33 years) were examined once weekly during two consecutive menstrual cycles using sonoelastography. Group 1 (n = 10) was not taking hormonal medication; group 2 (n = 12) was taking oral contraceptives.
Results-The breast parenchyma appeared softer than the dermis and harder than the adipose tissue, and elasticity varied over the menstrual cycle and between groups. Group 1 (no hormone intake) showed continuously increasing elasticity with relatively soft breast parenchyma in the menstrual and follicular phases and harder parenchyma in the luteal phase (P = .012). Group 2 (oral contraceptives) showed no statistically significant changes in breast parenchymal elasticity according to sonoelastography. The parenchyma was generally softer in group 1 compared with group 2 throughout the menstrual cycle (P = .033). The dermis, the subcutaneous adipose tissue, and the pectoralis major muscle showed no changes in elasticity. Comparison of measurements made during the first and the second menstrual cycles showed similar patterns of elasticity in both groups.
Conclusions-Sonoelastography is a reproducible method that can be used to determine the dependence of breast parenchyma elasticity on the menstrual cycle and on the intake of hormonal contraceptives.
The underlying motivation for the work carried out for this thesis was the growing need for more sustainable technologies. The aim was to synthesize a “palette” of functional nanomaterials using the established technique of hydrothermal carbonization (HTC). The incredible diversity of HTC was demonstrated together with small but steady advances in how HTC can be manipulated to tailor material properties for specific applications. Two main strategies were used to modify the materials obtained by HTC of glucose, a model precursor representing biomass. The first approach was the introduction of heteroatoms, or “doping” of the carbon framework. Sulfur was for the first time introduced as a dopant in hydrothermal carbon. The synthesis of sulfur and sulfur/nitrogen doped microspheres was presented whereby it was shown that the binding state of sulfur could be influenced by varying the type of sulfur source. Pyrolysis may additionally be used to tune the heteroatom binding states which move to more stable motifs with increasing pyrolysis temperature. Importantly, the presence of aromatic binding states in the as synthesized hydrothermal carbon allows for higher heteroatom retention levels after pyrolysis and hence more efficient use of dopant sources. In this regard, HTC may be considered as an “intermediate” step in the formation of conductive heteroatom doped carbon. To assess the novel hydrothermal carbons in terms of their potential for electrochemical applications, materials with defined nano-architectures and high surface areas were synthesized via templated, as well as template-free routes. Sulfur and/or nitrogen doped carbon hollow spheres (CHS) were synthesized using a polystyrene hard templating approach and doped carbon aerogels (CA) were synthesized using either the albumin directed or borax-mediated hydrothermal carbonization of glucose. Electrochemical testing showed that S/N dual doped CHS and aerogels derived via the albumin approach exhibited superior catalytic performance compared to solely nitrogen or sulfur doped counterparts in the oxygen reduction reaction (ORR) relevant to fuel cells. Using the borax mediated aerogel formation, nitrogen content and surface area could be tuned and a carbon aerogel was engineered to maximize electrochemical performance. The obtained sample exhibited drastically improved current densities compared to a platinum catalyst (but lower onset potential), as well as excellent long term stability. In the second approach HTC was carried out at elevated temperatures (550 °C) and pressure (50 bar), corresponding to the superheated vapor regime (htHTC). It was demonstrated that the carbon materials obtained via htHTC are distinct from those obtained via ltHTC and subsequent pyrolysis at 550 °C. No difference in htHTC-derived material properties could be observed between pentoses and hexoses. The material obtained from a polysaccharide exhibited a slightly lower degree of carbonization but was otherwise similar to the monosaccharide derived samples. It was shown that in addition to thermally induced carbonization at 550 °C, the SHV environment exhibits a catalytic effect on the carbonization process. The resulting materials are chemically inert (i.e. they contain a negligible amount of reactive functional groups) and possess low surface area and electronic conductivity which distinguishes them from carbon obtained from pyrolysis. Compared to the materials presented in the previous chapters on chemical modifications of hydrothermal carbon, this makes them ill-suited candidates for electronic applications like lithium ion batteries or electrocatalysts. However, htHTC derived materials could be interesting for applications that require chemical inertness but do not require specific electronic properties. The final section of this thesis therefore revisited the latex hard templating approach to synthesize carbon hollow spheres using htHTC. However, by using htHTC it was possible to carry out template removal in situ because the second heating step at 550 °C was above the polystyrene latex decomposition temperature. Preliminary tests showed that the CHS could be dispersed in an aqueous polystyrene latex without monomer penetrating into the hollow sphere voids. This leaves the stagnant air inside the CHS intact which in turn is promising for their application in heat and sound insulating coatings. Overall the work carried out in this thesis represents a noteworthy development in demonstrating the great potential of sustainable carbon materials.
The chemistry of water on alpha-alumina kinetics and nuclear quantum effects from first principles
(2012)
Water adsorption on an alumina (alpha-Al2O3) surface is studied here from first principles using periodic density functional theory in the generalized gradient approximation. Two different coverage regimes, low and high, are considered. For the low-coverage regime (with a coverage of 1/4 with respect to the number of coordinatively unsaturated Al sites), possible reactions at the surface such as dissociation, rotation, and diffusion of water and its fragments are investigated, using first principles thermodynamics and kinetics. A microkinetic model is set up with rates calculated from Eyring's transition state theory in order to cover a wide range of time scales. Special emphasis of this study is on the magnitude of quantum effects and on anharmonic corrections, particularly for reactions and dynamics. These have often been neglected in the past for water/alumina systems but can influence the system. This is particularly true for processes involving hydrogen atoms, where, for example, tunneling corrections to reaction rates are found to be important even at room temperature. For a higher-coverage regime (with a coverage of 2 ML), hydrogen dynamics becomes even more complex and is characterized, e.g., by concerted atom motion, strong anharmonicity, and delocalization. In this regime, classical molecular dynamics becomes questionable as well as quantum mechanical treatments based on the harmonic approximation.
Dielectric elastomers (DE) are soft polymer materials exhibiting large deformations under electrostatic stress. When a prestretched elastomer is stuck to a flat plastic frame, a complex structure that can be used as an actuator (DEA) is formed due to self-organization and energy minimization. Here, such a DEA was equipped with a ferroelectret film. Ferroelectrets are internally charged polymer foams or void-containing polymer-film systems combining large piezoelectricity with mechanical flexibility and elastic compliance. In their dielectric spectra, ferroelectrets show piezoelectric resonances that can be used to analyze their electromechanical properties. The antiresonance frequencies ( ) of ferroelectret films not only are directly related to their geometric parameters, but also are sensitive to the boundary conditions during measurement. In this paper, a fluoroethylenepropylene (FEP) ferroelectret film with tubular void channels was glued to a plastic frame prior to the formation of self-organized minimum-energy DEA structure. The dielectric resonance spectrum (DRS) of the ferroelectret film was measured in-situ during the actuation of the DEA under applied voltage. It is found that the antiresonance frequency is a monotropic function of the bending angle of the actuator. Therefore, the actuation of DEAs can be used to modulate the of ferroelectrets, while the can also be taken for in-situ diagnosis and for precise control of the actuation of the DEA. Combination of DEAs and ferroelectrets brings a number of possibilities for application.
Ionic liquids (ILs) on the basis of metal containing anions and/or cations are of interest for a variety of technical applications e.g., synthesis of particles, magnetic or thermochromic materials. We present the synthesis and the results of electron paramagnetic resonance (EPR) spectroscopic analyses of a series of some new potential ionic liquids based on tetrachloridocuprates(II), [CuCl4](2-), with different sterically demanding cations: hexadecyltrimethylammonium 1, tetradecyltrimethylammonium 2, tetrabutylammonium 3 and benzyltriethylammonium 4. The cations in the new compounds were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. The EPR hyperfine structure was not resolved. This is due to the exchange broadening, resulting from still incomplete separation of the paramagnetic Cu(II) centers. Nevertheless, the principal values of the electron Zeemann tensor (g parallel to and g perpendicular to) of the complexes could be determined. Even though the solid substances show slightly different colors, the UV/Vis spectra are nearly identical, indicating structural changes of the tetrachloridocuprate moieties between solid state and solution. The complexes have a promising potential e.g., as high temperature ionic liquids, as precursors for the formation of copper chloride particles or as catalytic paramagnetic ionic liquids.
Anthropogenic climate change is likely to cause continuing global sea level rise(1), but some processes within the Earth system may mitigate the magnitude of the projected effect. Regional and global climate models simulate enhanced snowfall over Antarctica, which would provide a direct offset of the future contribution to global sea level rise from cryospheric mass loss(2,3) and ocean expansion(4). Uncertainties exist in modelled snowfall(5), but even larger uncertainties exist in the potential changes of dynamic ice discharge from Antarctica(1,6) and thus in the ultimate fate of the precipitation-deposited ice mass. Here we show that snowfall and discharge are not independent, but that future ice discharge will increase by up to three times as a result of additional snowfall under global warming. Our results, based on an ice-sheet model(7) forced by climate simulations through to the end of 2500 (ref. 8), show that the enhanced discharge effect exceeds the effect of surface warming as well as that of basal ice-shelf melting, and is due to the difference in surface elevation change caused by snowfall on grounded versus floating ice. Although different underlying forcings drive ice loss from basal melting versus increased snowfall, similar ice dynamical processes are nonetheless at work in both; therefore results are relatively independent of the specific representation of the transition zone. In an ensemble of simulations designed to capture ice-physics uncertainty, the additional dynamic ice loss along the coastline compensates between 30 and 65 per cent of the ice gain due to enhanced snowfall over the entire continent. This results in a dynamic ice loss of up to 1.25 metres in the year 2500 for the strongest warming scenario. The reported effect thus strongly counters a potential negative contribution to global sea level by the Antarctic Ice Sheet.
Nuclear proteins play a central role in regulating gene expression. Their identification is important for understanding how the nuclear repertoire changes over time under different conditions. Nuclear proteins are often underrepresented in proteomic studies due to the frequently low abundance of proteins involved in regulatory processes. So far, only few studies describing the nuclear proteome of plant species have been published. Recently, the genome sequence of the unicellular green alga Chlamydomonas reinhardtii has been obtained and annotated, allowing the development of further detailed studies for this organism. However, a detailed description of its nuclear proteome has not been reported so far. Here, we present an analysis of the nuclear proteome of the sequenced Chlamydomonas strain cc503. Using LC-MS/MS, we identified 672 proteins from nuclei isolates with a maximum 1% peptide spectrum false discovery rate. Besides well-known proteins (e.g. histones), transcription factors and other transcriptional regulators (e.g. tubby and HMG) were identified. The presence of protein motifs in nuclear proteins was investigated by computational tools, and specific over-represented protein motifs were identified. This study provides new insights into the complexity of the nuclear environment and reveals novel putative protein targets for further studies of nuclear mechanisms.
In the late Palaeozoic fore-arc system of north-central Chile at latitudes 31-32 degrees S (from the west to the east) three lithotectonic units are telescoped within a short distance by a Mesozoic strikeslip event (derived peak P-T conditions in brackets): (1) the basally accreted Choapa Metamorphic Complex (CMC; 350-430 degrees C, 6-9 kbar), (2) the frontally accreted Arrayan Formation (AF; 280-320 degrees C, 4-6 kbar) and (3) the retrowedge basin of the Huentelauquen Formation (HF; 280-320 degrees C, 3-4 kbar). In the CMC, Ar-Ar spot ages locally date white-mica formation at peak P-T conditions and during early exhumation at 279-242 Ma. In a local garnet mica-schist intercalation (570-585 degrees C, 11-13 kbar) Ar-Ar spot ages refer to the ascent from the subduction channel at 307-274 Ma. Portions of the CMC were isobarically heated to 510-580 degrees C at 6.6-8.5 kbar. The age of peak P-T conditions in the AF can only vaguely be approximated at >= 310 Ma by relict fission-track ages consistent with the observation that frontal accretion occurred prior to basal accretion. Zircon fission-track dating indicates cooling below similar to 280 degrees C at similar to 248 Ma in the CMC and the AF, when a regional unconformity also formed. Ar-Ar white-mica spot ages in parts of the CMC and within the entire AF and HF point to heterogeneous resetting during Mesozoic extensional and shortening events at similar to 245-240 Ma, similar to 210-200 Ma, similar to 174-159 Ma and similar to 142-127 Ma. The zircon fission-track ages are locally reset at 109-96 Ma. All resetting of Ar-Ar white-mica ages is proposed to have occurred by in situ dissolution/precipitation at low temperature in the presence of locally penetrating hydrous fluids. Hence syn-and postaccretionary events in the fore-arc system can still be distinguished and dated in spite of its complex heterogeneous postaccretional overprint.
In the late Palaeozoic fore-arc system of north-central Chile at latitudes 31-32 degrees S (from the west to the east) three lithotectonic units are telescoped within a short distance by a Mesozoic strikeslip event (derived peak P-T conditions in brackets): (1) the basally accreted Choapa Metamorphic Complex (CMC; 350-430 degrees C, 6-9 kbar), (2) the frontally accreted Arrayan Formation (AF; 280-320 degrees C, 4-6 kbar) and (3) the retrowedge basin of the Huentelauquen Formation (HF; 280-320 degrees C, 3-4 kbar). In the CMC, Ar-Ar spot ages locally date white-mica formation at peak P-T conditions and during early exhumation at 279-242 Ma. In a local garnet mica-schist intercalation (570-585 degrees C, 11-13 kbar) Ar-Ar spot ages refer to the ascent from the subduction channel at 307-274 Ma. Portions of the CMC were isobarically heated to 510-580 degrees C at 6.6-8.5 kbar. The age of peak P-T conditions in the AF can only vaguely be approximated at >= 310 Ma by relict fission-track ages consistent with the observation that frontal accretion occurred prior to basal accretion. Zircon fission-track dating indicates cooling below similar to 280 degrees C at similar to 248 Ma in the CMC and the AF, when a regional unconformity also formed. Ar-Ar white-mica spot ages in parts of the CMC and within the entire AF and HF point to heterogeneous resetting during Mesozoic extensional and shortening events at similar to 245-240 Ma, similar to 210-200 Ma, similar to 174-159 Ma and similar to 142-127 Ma. The zircon fission-track ages are locally reset at 109-96 Ma. All resetting of Ar-Ar white-mica ages is proposed to have occurred by in situ dissolution/precipitation at low temperature in the presence of locally penetrating hydrous fluids. Hence syn-and postaccretionary events in the fore-arc system can still be distinguished and dated in spite of its complex heterogeneous postaccretional overprint.
The aim of this experimental study was to evaluate and compare the geochemical impact of pure and impure CO2 on rock forming minerals of possible CO2 storage reservoirs. This geochemical approach takes into account the incomplete purification of industrial captured CO2 and the related effects during injection, and provides relevant data for long-term storage simulations of this specific greenhouse gas. Batch experiments were conducted to investigate the interactions of supercritical CO2, brine and rock-forming mineral concentrates (albite, microcline, kaolinite, biotite, muscovite, calcite, dolomite and anhydrite) using a newly developed experimental setup. After up to 42 day (1000 h) experiments using pure and impure supercritical CO2 the dissolution and solution characteristics were examined by XRD, XRF, SEM and EDS for the solid, and ICP-MS and IC for the fluid reactants, respectively. Experiments with mixtures of supercritical CO2 (99.5 vol.%) and SO2 or NO2 impurities (0.5 vol.%) suggest the formation of H2SO4 and HNO3, reflected in pH values between 1 and 4 for experiments with silicates and anhydrite and between 5 and 6 for experiments with carbonates. These acids should be responsible for the general larger amount of cations dissolved from the mineral phases compared to experiments using pure CO2. For pure CO2 a pH of around 4 was obtained using silicates and anhydrite, and 7-8 for carbonates. Dissolution of carbonates was observed after both pure and impure CO2 experiments. Anhydrite was corroded by approximately 50 wt.% and gypsum precipitated during experiments with supercritical CO2 + NO2. Silicates do not exhibit visible alterations during all experiments but released an increasing amount of cations in the reaction fluid during experiments with impure CO2. Nonetheless, precipitated secondary carbonates could not be identified.
Apatite fission track and apatite and zircon (U-Th)/He ages were obtained from high- and ultra high-pressure rocks from the Kaghan Valley, Pakistan. Four samples from the high altitude northern parts of the valley yielded apatite fission track ages between 24.5 +/- 3.7 and 15.6 +/- 2.1 Ma and apatite (U-Th)/He ages between 21.0 +/- 0.6 and 5.3 +/- 0.2 Ma. These data record cooling of the formerly deeply-subducted high-grade metamorphic rocks induced by denudation and exhumation consistent with extension and back sliding along the reactivated, normal-acting Main Mantle Thrust. Overlap at around 10 Ma between fission track and (U-Th)/He ages is recognised at one location (Besal) showing that fast cooling occurred due to brittle reactivation of a former thrust fault. Widespread Miocene cooling is also evident in adjacent areas to the west (Deosai Plateau, Tso Moran), most likely related to uplift and unroofing linked to continued underplating of the Indian lower crust beneath Ladakh and Kohistan in the Late Eocene to Oligocene. In the southernmost part of the study area, near Naran, two significantly younger Late Miocene to Pliocene apatite fission track ages of 7.6 +/- 2.1 to 4.0 +/- 0.5 Ma suggest a spatial and temporal separation of exhumation processes. These younger ages are best explained by enhanced Late Miocene uplift and erosion driven by thrusting along the Main Boundary Thrust.
Coastal regions of the North East Atlantic and Mediterranean Seas have four known species of driftwood talitrids. Records are extremely scanty, often limited to the type locality and dating to 1950. We were able to study three of them, all belonging to the genus Macarorchestia, using fresh and archived samples including type material. Allometric and molecular analyses support: (1) a close relationship among all the three classically defined Macarorchestia species, (2) Macarorchestia was well separated from non-driftwood taxa, and (3) a putative new driftwood talitrid discovered during this study was not closely related to Macarorchestia. Genetic divergence between the new species and Macarorchestia remyi is as high as the average distance among a number of talitrid species included in the study for comparison. A key is provided to identify all three of the presently known species of Macarorchestia, using morphological characters employed in the allometric study.
Building blocks for oligospiroketal (OSK) rods and evaluation of their influence on rod rigidity
(2012)
We report on the synthesis of three new sleeves and their incorporation in OSK rods. The structures of these sleeves are based on neo-inositol, terephthalaldehyde diacetals, and indacene. To quantify the influence of the sleeves on rod rigidity, we applied the worm-like chain (WLC) model on the new rods and found that this approach is rather disappointing. As the chief cause of this result, we assume that the rigidity of typical molecular rods largely exceeds the rigidity of polymers, which were successfully described by the WLC model. Alternatively, we suggest quantifying the rigidity of molecular rods by fitting an empirical function on the end-to-end distance distribution curve obtained by MD simulations. After checking various function types, the Levy-Martin function proved to be most suitable for this purpose. On the basis of this function, we defined the Levy-Martin parameter and suggest using this parameter for the characterization of the rigidity of molecular rods.