How different is water crystallization from polymer crystallization under confinement?

Ziel der vorliegenden Dissertation war es, Einblicke in das Kristallisationsverhalten weicher Materie („soft matter“), wie verschiedener Polymere oder Wasser, unter räumlicher Einschränkung („confinement“) zu erlangen. Dabei sollte untersucht werden, wie, weshalb und wann die Kristallisation in nanoporösen Strukturen eintritt. Desweiteren ist Kristallisation weicher Materie in nanoporösen Strukturen nicht nur aus Aspekten der Grundlagenforschung von großem Interesse, sondern es ergeben sich zahlreiche praktische Anwendungen. Durch die gezielte Steuerung der Kristallinität von Polymeren könnten somit Materialien mit verschiendenen mechanischen und optischen Eigenschaften erhalten werden. Desweiteren wurde auch räumlich eingeschränktes Wasser untersucht. Dieses spielt eine wichtige Rolle in der Molekularbiologie, z.B. für das globuläre Protein, und als Wolkenkondensationskeime in der Atmosphärenchemie und Physik. Auch im interstellaren Raum ist eingeschränktes Wasser in Form von Eispartikeln anzutreffen. Die Kristallisation von eingeschränktem Wasser zu verstehen und zu beeinflussen ist letztlich auch für die Haltbarkeit von Baumaterialien wie etwa Zement von großem Interesse.rnUm dies zu untersuchen wird Wasser in der Regel stark abgekühlt und das Kristallisationsverhalten in Abhängigkeit des Volumens untersucht. Dabei wurde beobachtet, dass Mikro- bzw. Nanometer große Volumina erst ab -38 °C bzw. -70 °C kristallisieren. Wasser unterliegt dabei in der Regel dem Prozess der homogenen Nukleation. In der Regel gefriert Wasser aber bei höheren Temperaturen, da durch Verunreinigungen eine vorzeitige, heterogene Nukleation eintritt.rnDie vorliegende Arbeit untersucht die sachdienlichen Phasendiagramme von kristallisierbaren Polymeren und Wasser unter räumlich eingeschränkten Bedingungen. Selbst ausgerichtetes Aluminiumoxid (AAO) mit Porengrößen im Bereich von 25 bis 400 nm wurden als räumliche Einschränkung sowohl für Polymere als auch für Wasser gewählt. Die AAO Nanoporen sind zylindrisch und parallel ausgerichtet. Außerdem besitzen sie eine gleichmäßige Porenlänge und einen gleichmäßigen Durchmesser. Daher eignen sie sich als Modelsystem um Kristallisationsprozesse unter wohldefinierter räumlicher Einschränkung zu untersuchen.rnEs wurden verschiedene halbkristalline Polymere verwendet, darunter Poly(ethylenoxid), Poly(ɛ-Caprolacton) und Diblockcopolymere aus PEO-b-PCL. Der Einfluss der Porengröße auf die Nukleation wurde aus verschiedenen Gesichtspunkten untersucht: (i) Einfluss auf den Nukleationmechanismus (heterogene gegenüber homogener Nukleation), (ii) Kristallorientierung und Kristallinitätsgrad und (iii) Zusammenhang zwischen Kristallisationstemperatur bei homogener Kristallisation und Glasübergangstemperatur.rnEs konnte gezeigt werden, dass die Kristallisation von Polymeren in Bulk durch heterogene Nukleation induziert wird und das die Kristallisation in kleinen Poren hauptsächlich über homogene Nukleation mit reduzierter und einstellbarer Kristallinität verläuft und eine hohe Kristallorientierung aufweist. Durch die AAOs konnte außerdem die kritische Keimgröße für die Kristallisation der Polymere abgeschätzt werden. Schließlich wurde der Einfluss der Polydispersität, von Oligomeren und anderen Zusatzstoffen auf den Nukleationsmechanismus untersucht.rn4rnDie Nukleation von Eis wurde in den selben AAOs untersucht und ein direkter Zusammenhang zwischen dem Nukleationstyp (heterogen bzw. homogen) und der gebildeten Eisphase konnte beobachtet werden. In größeren Poren verlief die Nukleation heterogen, wohingegen sie in kleineren Poren homogen verlief. Außerdem wurde eine Phasenumwandlung des Eises beobachtet. In den größeren Poren wurde hexagonales Eis nachgewiesen und unter einer Porengröße von 35 nm trat hauptsächlich kubisches Eis auf. Nennenswerter Weise handelte es sich bei dem kubischem Eis nicht um eine metastabile sondern eine stabile Phase. Abschließend wird ein Phasendiagramm für räumlich eingeschränktes Wasser vorgeschlagen. Dieses Phasendiagramm kann für technische Anwendungen von Bedeutung sein, so z.B. für Baumaterial wie Zement. Als weiteres Beispiel könnten AAOs, die die heterogene Nukleation unterdrücken (Porendurchmesser ≤ 35 nm) als Filter für Reinstwasser zum Einsatz kommen.rnNun zur Anfangs gestellten Frage: Wie unterschiedlich sind Wasser und Polymerkristallisation voneinander unter räumlicher Einschränkung? Durch Vergleich der beiden Phasendiagramme kommen wir zu dem Schluss, dass beide nicht fundamental verschieden sind. Dies ist zunächst verwunderlich, da Wasser ein kleines Molekül ist und wesentlich kleiner als die kleinste Porengröße ist. Wasser verfügt allerdings über starke Wasserstoffbrückenbindungen und verhält sich daher wie ein Polymer. Daher auch der Name „Polywasser“.

Diffusion-driven transport in clayrock formations

Clay mineral-rich sedimentary formations are currently under investigation to evaluate their potential use as host formations for installation of deep underground disposal facilities for radioactive waste (e.g. Boom Clay (BE), Opalinus Clay (CH), Callovo-Oxfordian argillite (FR)). The ultimate safety of the corresponding repository concepts depends largely on the capacity of the host formation to limit the flux towards the biosphere of radionuclides (RN) contained in the waste to acceptably low levels. Data for diffusion-driven transfer in these formations shows extreme differences in the measured or modelled behaviour for various radionuclides, e. g. between halogen RN (Cl-36, I-129) and actinides (U-238,U-235, Np-237, Th-232, etc.), which result from major differences between RN of the effects on transport of two phenomena: diffusion and sorption. This paper describes recent research aimed at improving understanding of these two phenomena, focusing on the results of studies carried out during the EC Funmig IP on clayrocks from the above three formations and from the Boda formation (HU). Project results regarding phenomena governing water, cation and anion distribution and mobility in the pore volumes influenced by the negatively-charged surfaces of clay minerals show a convergence of the modelling results for behaviour at the molecular scale and descriptions based on electrical double layer models. Transport models exist which couple ion distribution relative to the clay-solution interface and differentiated diffusive characteristics. These codes are able to reproduce the main trends in behaviour observed experimentally, e.g. D-e(anion) < D-e(HTO) < D-e(cation) and D-e(anion) variations as a function of ionic strength and material density. These trends are also well-explained by models of transport through ideal porous matrices made up of a charged surface material. Experimental validation of these models is good as regards monovalent alkaline cations, in progress for divalent electrostatically-interacting cations (e.g. Sr2+) and still relatively poor for 'strongly sorbing', high K-d cations. Funmig results have clarified understanding of how clayrock mineral composition, and the corresponding organisation of mineral grain assemblages and their associated porosity, can affect mobile solute (anions, HTO) diffusion at different scales (mm to geological formation). In particular, advances made in the capacity to map clayrock mineral grain-porosity organisation at high resolution provide additional elements for understanding diffusion anisotropy and for relating diffusion characteristics measured at different scales. On the other hand, the results of studies focusing on evaluating the potential effects of heterogeneity on mobile species diffusion at the formation scale tend to show that there is a minimal effect when compared to a homogeneous property model. Finally, the results of a natural tracer-based study carried out on the Opalinus Clay formation increase confidence in the use of diffusion parameters measured on laboratory scale samples for predicting diffusion over geological time-space scales. Much effort was placed on improving understanding of coupled sorption-diffusion phenomena for sorbing cations in clayrocks. Results regarding sorption equilibrium in dispersed and compacted materials for weakly to moderately sorbing cations (Sr2+, Cs+, Co2+) tend to show that the same sorption model probably holds in both systems. It was not possible to demonstrate this for highly sorbing elements such as Eu(III) because of the extremely long times needed to reach equilibrium conditions, but there does not seem to be any clear reason why such elements should not have similar behaviour. Diffusion experiments carried out with Sr2+, Cs+ and Eu(III) on all of the clayrocks gave mixed results and tend to show that coupled diffusion-sorption migration is much more complex than expected, leading generally to greater mobility than that predicted by coupling a batch-determined K-d and Ficks law based on the diffusion behaviour of HTO. If the K-d measured on equivalent dispersed systems holds as was shown to be the case for Sr, Cs (and probably Co) for Opalinus Clay, these results indicate that these cations have a D-e value higher than HTO (up to a factor of 10 for Cs+). Results are as yet very limited for very moderate to strongly sorbing species (e.g. Co(II), Eu(III), Cu(II)) because of their very slow transfer characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

A Preliminary Investigation of Chromite

The purpose of this thesis was to study the effects of cryolite and a mixture of cryolite and aluminum oxide on a chromite concentrate with special reference to the ability to break the bond between the ferrous iron and chromic oxide in the chromite.

Characterization of Optically Stimulated Luminescent Detectors in Photon & Proton Beams for Use in Anthropomorphic Phantoms

This study investigated characteristics of optically stimulated luminescent detectors (OSLDs) in protons, allowing comparison to thermoluminescent detectors, and to be implemented into the Radiological Physics Center’s (RPC) remote audit quality assurance program for protons, and for remote anthropomorphic phantom irradiations. The OSLDs used were aluminum oxide (Al2O3:C) nanoDots from Landauer, Inc. (Glenwood, Ill.) measuring 10x10x2 mm3. A square, 20(L)x20(W)x0.5(H) cm3 piece of solid water was fabricated with pockets to allow OSLDs and TLDs to be irradiated simultaneously and perpendicular to the beam. Irradiations were performed at 5cm depth in photons, and in the center of a 10 cm SOBP in a 200MeV proton beam. Additionally, the Radiological Physics Center’s anthropomorphic pelvic phantom was used to test the angular dependence of OSLDs in photons and protons. A cylindrical insert in the phantom allows the dosimeters to be rotated to any angle with a fixed gantry angle. OSLDs were irradiated at 12 angles between 0 and 360 degrees. The OSLDs were read out with a MicroStar reader from Landauer, Inc. Dose response indicates that at angles where the dosimeter is near parallel with the radiation beam response is reduced slightly. Measurements in proton beams do not show significant angular dependence. Post-irradiation fading of OSLDs was studied in proton beams to determine if the fading was different than that of photons. The fading results showed no significant difference from results in photon beams. OSLDs and TLDs are comparable within 3% in photon beams and a correction factor can be posited for proton beams. With angular dependence characteristics defined, OSLDs can be implemented into multiple-field treatment plans in photons and protons and used in the RPC’s quality assurance program.

Reduction of cement leakage by sequential PMMA application in a vertebroplasty model

PURPOSE Leakage is the most common complication of percutaneous cement augmentation of the spine. The viscosity of the polymethylmethacrylate (PMMA) cement is strongly correlated with the likelihood of cement leakage. We hypothesized that cement leakage can be reduced by sequential cement injection in a vertebroplasty model. METHODS A standardized vertebral body substitute model, consisting of aluminum oxide foams coated by acrylic cement with a preformed leakage path, simulating a ventral vein, was developed. Three injection techniques of 6 ml PMMA were assessed: injection in one single step (all-in-one), injection of 1 ml at the first and 5 ml at the second step with 1 min latency in-between (two-step), and sequential injection of 0.5 ml with 1-min latency between the sequences (sequential). Standard PMMA vertebroplasty cement was used; each injection type was tested on ten vertebral body substitute models with two possible leakage paths per model. Leakage was assessed by radiographs using a zonal graduation: intraspongious = no leakage and extracortical = leakage. RESULTS The leakage rate was significantly lower in the "sequential" technique (2/20 leakages) followed by "two-step" (15/20) and "all-in-one" (20/20) techniques (p < 0.001). The RR for a cement leakage was 10.0 times higher in the "all-in-one" compared to the "sequential" group (95 % confidence intervals 2.7-37.2; p < 0.001). CONCLUSIONS The sequential cement injection is a simple approach to minimize the risk for leakage. Taking advantage of the temperature gradient between body and room temperature, it is possible to increase the cement viscosity inside the vertebra while keeping it low in the syringe. Using sequential injection of small cement volumes, further leakage paths are blocked before further injection of the low-viscosity cement.

Two pre-treatments for bonding to non-carious cervical root dentin

Purpose: To investigate the effect of airborne-particle abrasion or diamond bur preparation as pretreatment steps of non-carious cervical root dentin regarding substance loss and bond strength. Methods: 45 dentin specimens produced from crowns of extracted human incisors by grinding the labial surfaces with silicon carbide papers (control) were treated with one of three adhesive systems (Group 1A-C; A: OptiBond FL, B: Clearfil SE Bond, or C: Scotchbond Universal; n=15/adhesive system). Another 135 dentin specimens (n=15/group) produced from the labial, non-carious cervical root part of extracted human incisors were treated with one of the adhesive systems after either no pre-treatment (Group 2A-C), pre-treatment with airborne-particle abrasion (CoJet Prep and 50 µm aluminum oxide powder; Group 3A-C), or pre-treatment with diamond bur preparation (40 µm grit size; Group 4A-C). Substance loss caused by the pre-treatment was measured in Groups 3 and 4. After treatment with the adhesive systems, resin composite was applied and all specimens were stored (37°C, 100% humidity, 24 hours) until measurement of microshear bond strength (µSBS). Data were analyzed with a nonparametric ANOVA followed by Kruskal-Wallis and Wilcoxon rank sum tests (level of significance: alpha=0.05). Results: Overall substance loss was significantly lower in Group 3 (median: 19 µm) than in Group 4 (median: 113 µm; p<0.0001). There were no significant differences in µSBS between the adhesive systems (A-C) in Group 1, Group 3, and Group 4 (p>=0.133). In Group 2, OptiBond FL (Group 2A) and Clearfil SE Bond (Group 2B) yielded significantly higher µSBS than Scotchbond Universal (Group 2C; p<=0.032). For OptiBond FL and Clearfil SE Bond, there were no significant differences in µSBS between the ground crown dentin and the non-carious cervical root dentin regardless of any pre-treatment of the latter (both p=0.661). For Scotchbond Universal, the µSBS to non-carious cervical root dentin without pre-treatment was significantly lower than to ground crown dentin and to non-carious cervical root dentin pre-treated with airborne-particle abrasion or diamond bur preparation p<=0.014).

Structural determinants of subunit -subunit interactions and subcellular localization of the calcium /calmodulin -dependent protein kinase II

The multifunctional Ca$\sp{2+}$/calmodulin-dependent protein kinase II (CaM kinase) is a Ser/Thr directed protein kinase that participates in diverse Ca$\sp{2+}$ signaling pathways in neurons. The function of CaM kinase depends upon the ability of subunits to form oligomers and to interact with other proteins. Oligomerization is required for autophosphorylation which produces significant functional changes that include Ca$\sp{2+}$/calmodulin-independent activity and calmodulin trapping. Associations with other proteins localize CaM kinase to specific substrates and effectors which serves to optimize the efficiency and speed of signal transduction. In this thesis, we investigate the interactions that underlie the appropriate positioning of CaM kinase activity in cells. We demonstrate that the subcellular distribution of CaM kinase is dynamic in hippocampal slices exposed to anoxic/aglycemic insults and to high K$\sp{+}$-induced depolarization. We determine the localization of CaM kinase domains expressed in neurons and PC-12 cells and find that the C-terminal domain of the $\alpha$ subunit is necessary for localization to dendrites. Moreover, monomeric forms of the enzyme gain access to the nucleus. Attempts made to identify novel CaM kinase binding proteins using the yeast two-hybrid system resulted in the isolation of hundreds of positive clones. Those that have been sequenced are identical to CaM kinase isoforms. Finally, we report the discovery of specific regions within the C-terminal domain that are necessary and sufficient for subunit-subunit interactions. Differences between the $\alpha$ and $\beta$ isoforms were discovered that indicate unique structural requirements for oligomerization. A model for how CaM kinase subunits interact to form holoenzymes and how structural heterogeneity might influence CaM kinase function is presented. ^

Depth tie points and ages of IODP Site 306-U1314

Integrated Ocean Drilling Program (IODP) Site U1314 of the North Atlantic is a critical sedimentary archive record of subpolar deep water from the southern Gardar Drift for which we derived an age model of orbital resolution for the last 1.8 Ma. This chronology combined with high-resolution (cm scale) X-ray fluorescence core scanning measurements of major elements allows tracking changes in terrigenous provenance during the last 1.1 Ma. Low Potassium to Titanium (K/Ti) ratios reflect enhanced transport of basalt-derived titanomagnetites during warm climate intervals, while high K/Ti ratios indicate a dominance of acidic sediment sources typical for glacial and stadial events. Changes in K/Ti and magnetic concentration at Site 1314 are coeval with fluctuations in smectite content and grain size data from nearby piston cores, suggesting that the provenance changes are mainly controlled by variable flow of the Iceland-Scotland Overflow Water, an important branch of North Atlantic Deep Water. Furthermore, K/Ti variations on orbital time scales show a striking similarity to the deep sea d13C record from ODP Site 607. Pervasive features of the K/Ti time series during and after the Mid-Pleistocene Transition are suborbital changes similar to Dansgaard/Oeschger and Bond oscillations that appear to be strongly amplified during ice growth phases when global benthic d18O was within the range of ~4.1-4.6 per mil. The strong increase in variability of sediment provenance and subsequently deep hydrography at benthic d18O values below ~4.1 suggests that the extent of glaciations and, therefore, sea level corresponding to this value constitutes an important physical threshold that was persistent at least for the last 1.1 Ma.

Zircon U-Pb and Hf-O analysis of porphyries from the Duolong porphyry Cu-Au deposit in the Bangongco copper belt, central Tibet

The Duolong porphyry Cu-Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au), which is related to the granodiorite porphyry and the quartz-diorite porphyry from the Bangongco copper belt in central Tibet, formed in a continental arc setting. Here, we present the zircon U-Pb ages, geochemical whole-rock, Sr-Nd whole-rock and zircon in-situ Hf-O isotopic data for the Duolong porphyries. Secondary ion mass spectrometry (SIMS) zircon U-Pb analyses for six samples yielded consistent ages of ~118 Ma, indicating a Cretaceous formation age. The Duolong porphyries (SiO2 of 58.81-68.81 wt.%, K2O of 2.90-5.17 wt.%) belong to the high-K calc-alkaline series. They show light rare earth element (LREE)-enriched distribution patterns with (La/Yb)N = 6.1-11.7, enrichment in large ion lithophile elements (e.g., Cs, Rb, and Ba) and depletion of high field strength elements (e.g., Nb), with negative Ti anomalies. All zircons from the Duolong porphyries share relatively similar Hf-O isotopic compositions (d18O=5.88-7.27 per mil; eHf(t)=3.6-7.3), indicating that they crystallized from a series of cogenetic melts with various degrees of fractional crystallization. This, along with the general absence of older inherited zircons, rules out significant crustal contamination during zircon growth. The zircons are mostly enriched in d18O relative to mantle values, indicating the involvement of an 18O-enriched crustal source in the generation of the Duolong porphyries. Together with the presence of syn-mineralization basaltic andesite, the mixing between silicic melts derived from the lower crust and evolved H2O-rich mafic melts derived from the metsomatizied mantle wedge, followed by subsequent fractional crystallization (FC) and minor crustal contamination in the shallow crust, could well explain the petrogenesis of the Duolong porphyries. Significantly, the hybrid melts possibly inherited the arc magma characteristics of abundant F, Cl, Cu, and Au elements and high oxidation state, which contributed to the formation of the Duolong porphyry Cu-Au deposit.

Table A1 LA-ICP-MS zircon U-Pb data of Laoniushan granitoids

The NWW-striking Qinling Orogen formed in the Triassic by collision between the North China and Yangtze Cratons. Triassic granitoid intrusions, mostly middle- to high-K, calc-alkaline in composition, are widespread in this orogen, but contemporaneous intrusions are rare in the southern margin of the North China Craton, an area commonly considered as the hinterland belt of the orogen. In this paper, we report zircon U-Pb ages, elemental geochemistry, and Sr-Nd-Hf isotope data for the Laoniushan granitoid complex that was emplaced in the southern margin of the North China Craton. Zircon U-Pb dating shows that the complex was emplaced in the late Triassic (228±1 to 215±4 Ma), indicating that it is part of the post-collisional magmatism in the Qinling Orogen. The complex consists of, from early to late, biotite monzogranite, quartz diorite, quartz monzonite, and hornblende monzonite, which have a wide compositional range, e.g., SiO2=55.9-70.6 wt%, K2O+Na2O=6.6-10.2 wt%, and Mg# of 24 to 54. Rocks of the biotite monzogranite have high Al2O3(15.5-17.4 wt%), Sr(396-1398 ppm) and Ba(1284-3993 ppm) contents and La/Yb(mostly 14-30) and Sr/Y(mostly 40-97) ratios, but low Yb(mostly 1.3-1.6 ppm) and Y(mostly14-19 ppm) contents, features typical of adakite. The quartz monzonite, hornblende monzonite and quartz diorite have a shoshonitic affinity, with K2O up to 5.58 wt% and K2O/Na2O ratios averaging 1.4. The rocks are characterized by strong LREE/HREE fractionation in chondrite-normalized REE pattern, without obvious Eu anomalies, and show enrichment in large ion lithophile elements but depletion in high field strength elements (Nb, Ta, Ti). The biotite monzogranite (228 Ma) has initial 87Sr/86Sr ratios of 0.7061 to 0.7067, eNd(t) values of -9.2 to -12.6, and ?Hf(t) values of -9.0 to -15.1; whereas the shoshonitic granitoids (mainly 217-215 Ma) have similar initial 87Sr/86Sr ratios (0.7065 to 0.7075) but more radiogenic eNd(t) (-12.4 to -17.0) and eHf(t) (-14.1 to -17.0). The Sr-Nd-Hf isotope data indicate that the rocks were likely generated by partial melting of an ancient lower continental crust with heterogeneous compositions, as partly confirmed by the widespread presence of the early Paleoproterozoic inherited zircons. Mafic microgranular enclaves (MMEs), characterized by fine-grained igneous textures and an abundance of acicular apatites, are common in the Laoniushan complex. Compared with the host rocks, they have lower SiO2 (48.6-53.7 wt.%) and higher Mg# (51-56), Cr (122-393 ppm), and Ni (24-79 ppm), but equivalent Sr-Nd isotope compositions, indicating that the MMEs likely originated from an ancient enriched lithospheric mantle. The abundance of MMEs in the granitoid intrusions suggests that magma mixing plays an important role in the generation of the Laoniushan complex. Collectively, it is suggested that the Laoniushan complex was a product of post-collisional magmatism related to lithospheric extension following slab break-off. Formation of the adakitic and shoshonitic intrusions in the Laoniushan complex indicates that the Qinling Orogen had evolved into a post-collisional setting by about 230-210 Ma.

Physical properties of four profiles from the Triassic in Germany

The Norian Steinmergel-Keuper (SMK) represents a low-latitude cyclically-bedded playa system of the Mid-German Basin. We investigated a drilling site (core Morsleben) and sections from marginal positions. Dolomite/red mudstone beds form rhythmic alternations that were associated with varying monsoon activity. Hence, low K/Al ratios of dolomite beds suggest increased chemical weathering of the crystalline hinterland and therefore increased monsoonal rainfall. High K/Al ratios in red mudstone beds reflect increased physical weathering of the hinterlands during dryer periods. Dolomite layers reflect the lake stage (maximum monsoon) while red mudstones indicate the dry phase (minimum monsoon) of the playa cycle. We distinguished five major types of cyclic facies alternations, representing specific facies zones in the playa system. We have implemented spectrophotometry as a tool for high-resolution cyclostratigraphy. The dense sampling increment (up to 1 cm) allows for the recognition of all orbital frequencies. Sediment colour profiles reveal striking hierarchical cycles from semi-precession (SP, 99 kyr) over precession (P, 19.8 kyr) and obliquity (O, 36 kyr) to eccentricity (E1-2 109 kyr; E3, 413 kyr). A significant about 2 Myr-signal is attributed to the longer-term eccentricity E4. One monsoonal (precession) cycle includes two carbonate precipitation events. We propose that stratified mudstone and red mudstone are associated with maximum and minimum monsoon during the transition of the solstices in perihelion and aphelion, respectively. The two carbonate precipitation events were most likely created when equinoxes were in perihelion and aphelion, respectively. A sedimentary semi-precession response cycle is a novel finding for the Norian strata. The obliquity signal is attributed to incoming atmospheric moisture from the northeast of the SMK basin. The E4 cycle controls lake-level changes over long times. Apparently, E4 is responsible whether or not a threshold value is crossed. Bundles of 109 kyr and 413 kyr in red mudstones suggest a dry system with reduced monsoonal activity. In contrast, humid periods reveal thick layers of dolomite beds, indicating that during those intervals the monsoonal activity was strong enough to prevent the playa system from drying out completely.

Laser-fired contact optimization in c-Si solar cells

In this work we study the optimization of laser-fired contact (LFC) processing parameters, namely laser power and number of pulses, based on the electrical resistance measurement of an aluminum single LFC point. LFC process has been made through four passivation layers that are typically used in c-Si and mc-Si solar cell fabrication: thermally grown silicon oxide (SiO2), deposited phosphorus-doped amorphous silicon carbide (a-SiCx/H(n)), aluminum oxide (Al2O3) and silicon nitride (SiNx/H) films. Values for the LFC resistance normalized by the laser spot area in the range of 0.65–3 mΩ cm2 have been obtained

Intracellular misrouting and abnormal secretion of adrenocorticotropin and growth hormone in Cpefat mice associated with a carboxypeptidase E mutation

Cpefat mice carry a mutation in the carboxypeptidase E/H gene which encodes an exopeptidase that removes C-terminal basic residues from endoproteolytically cleaved hormone intermediates. These mice have endocrine disorders including obesity, infertility, and hyperproinsulinemia–diabetes syndrome, but the etiology remains an enigma. Because studies have identified membrane carboxypeptidase E as a sorting receptor for targeting prohormones to the regulated secretory pathway for processing and secretion, the intracellular routing and secretion of pro-opiomelanocortin/adrenocorticotropin and growth hormone from anterior pituitary cells were investigated in Cpefat mice. In Cpefat mice, pro-opiomelanocortin was accumulated 24-fold above normal animals in the pituitary and it was poorly processed to adrenocorticotropin. Furthermore, pro-opiomelanocortin was secreted constitutively at high levels, showing no response to stimulation by corticotropin-releasing hormone. Similarly, growth hormone release was constitutive and did not respond to high K+ stimulation. Both pro-opiomelanocortin and growth hormone levels were elevated in the circulation of Cpefat mice versus normal mice. These data provide evidence that the lack of carboxypeptidase E, the sorting receptor, results in the intracellular misrouting and secretion of pro-opiomelanocortin and growth hormone via the constitutive pathway in the pituitary of Cpefat mice.

Preferential Zn2+ influx through Ca2+-permeable AMPA/kainate channels triggers prolonged mitochondrial superoxide production

Synaptically released Zn2+ can enter and cause injury to postsynaptic neurons. Microfluorimetric studies using the Zn2+-sensitive probe, Newport green, examined levels of [Zn2+]i attained in cultured cortical neurons on exposure to N-methyl-d-asparte, kainate, or high K+ (to activate voltage-sensitive Ca2+ channels) in the presence of 300 μM Zn2+. Indicating particularly high permeability through Ca2+-permeable α-amino3-hydroxy-5-methyl-4-isoxazolepropionic-acid/kainate (Ca-A/K) channels, micromolar [Zn2+]i rises were observed only after kainate exposures and only in neurons expressing these channels [Ca-A/K(+) neurons]. Further studies using the oxidation-sensitive dye, hydroethidine, revealed Zn2+-dependent reactive oxygen species (ROS) generation that paralleled the [Zn2+]i rises, with rapid oxidation observed only in the case of Zn2+ entry through Ca-A/K channels. Indicating a mitochondrial source of this ROS generation, hydroethidine oxidation was inhibited by the mitochondrial electron transport blocker, rotenone. Additional evidence for a direct interaction between Zn2+ and mitochondria was provided by the observation that the Zn2+ entry through Ca-A/K channels triggered rapid mitochondrial depolarization, as assessed by using the potential-sensitive dye tetramethylrhodamine ethylester. Whereas Ca2+ influx through Ca-A/K channels also triggers ROS production, the [Zn2+]i rises and subsequent ROS production are of more prolonged duration.