Coil-ring-coil block copolymers as building blocks of supramolecular hollow cylindrical brushes

This work describes the synthesis of a new class of rod-coil block copolymers, oligosubstituted shape persistent macrocycles, (coil-ring-coil block copolymers), and their behavior in solution and in the solid state.The coil-ring-coil block copolymers are formed by nanometer sized shape persistent macrocycles based on the phenyl-ethynyl backbone as rigid block and oligomers of polystyrene or polydimethylsiloxane as flexible blocks. The strategy that has been followed is to synthesize the macrocycles with an alcoholic functionality and the polymer carboxylic acids independently, and then bind them together by esterification. The ester bond is stable and relatively easy to form.The synthesis of the shape persistent macrocycles is based on two separate steps. In the first step the building blocks of the macrocycles are connected by Hagiara-Sogonaschira coupling to form an 'half-ring' as precursor, that contains two free acetylenes. In the second step the half-ring is cyclized by forming two sp-sp bonds via a copper-catalyzed Glaser coupling under pseudo-high-dilution conditions. The polystyrene carboxylic acid was prepared directly by siphoning the living anionic polymer chain into a THF solution, saturated with CO2, while the polydimethylsiloxane carboxylic acid was obtained by hydrosilylating an unsaturated benzylester with an Si-H terminated polydimethylsiloxane, and cleavage of the ester. The carbodiimide coupling was found to be the best way to connect macrocycles and polymers in high yield and high purity.The polystyrene-ring-polystyrene block copolymers are, depending on the molecular weight of the polystyrene, lyotropic liquid crystals in cyclohexane. The aggregation behavior of the copolymers in solution was investigated in more detail using several technique. As a result it can be concluded that the polystyrene-ring-polystyrene block copolymers can aggregate into hollow cylinder-like objects with an average length of 700 nm by a combination of shape complementary and demixing of rigid and flexible polymer parts. The resulting structure can be described as supramolecular hollow cylindrical brush.If the lyotropic solution of the polystyrene-ring-polystyrene block copolymers are dried, they remain birefringent indicating that the solid state has an ordered structure. The polydimethylsiloxane-ring-polydimethylsiloxane block copolymers are more or less fluid at room temperature, and are all birefringent (termotropic liquid crystals) as well. This is a prove that the copolymers are ordered in the fluid state. By a careful investigation using electron diffraction and wide-angle X-ray scattering, it has been possible to derive a model for the 3D-order of the copolymers. The data indicate a lamella structure for both type of copolymers. The macrocycles are arranged in a layer of columns. These crystalline layers are separated by amorphous layers which contain the polymers substituents.

Modeling Yield Surfaces of Various Structural Shapes

This study investigates the possibility of custom fitting a widely accepted approximate yield surface equation (Ziemian, 2000) to the theoretical yield surfaces of five different structural shapes, which include wide-flange, solid and hollow rectangular, and solid and hollow circular shapes. To achieve this goal, a theoretically “exact” but overly complex representation of the cross section’s yield surface was initially obtained by using fundamental principles of solid mechanics. A weighted regression analysis was performed with the “exact” yield surface data to obtain the specific coefficients of three terms in the approximate yield surface equation. These coefficients were calculated to determine the “best” yield surface equation for a given cross section geometry. Given that the exact yield surface shall have zero percentage of concavity, this investigation evaluated the resulting coefficient of determination (

An Analysis Of U.S.- Economic Policy Toward Chile During The Cold War

This examination of U.S. economic policy directed toward Chile centered on the political and economic changes that occurred within Chile between 1960 and 1988. During this time, U.S. economic policy directed toward Chile was crafted by members of the American government uneasy with Cold War concerns with the most important of which being the spread of Communism throughout the globe. By viewing U.S. policy toward Chile through this Cold War lens, this thesis explores the different ways in which economic policy was used to advance the political and economic goals within not only Chile, but also Latin America as a whole. The Cold Warriors that crafted and enacted these economic policies were motivated by a variety of factors, and influenced by events outside of their control. From President John F. Kennedy to Ronald Reagan, American policymakers utilized economic policy as a means to achieve regional goals. This project sheds light on an understudied section of U.S. foreign policy history by exploring the way that economic policy helped achieve Cold War objectives in the Southern Cone.

Mineralogy and isotopic composition of sulfur in ODP Hole 118-735B gabbros

Sulfide mineralogy, sulfur contents, and sulfur isotopic compositions were determined for samples from the 500-m gabbroic section of Ocean Drilling Program Hole 735B in the southwest Indian Ocean. Igneous sulfides (pyrrhotite, chalcopyrite, pentlandite, and troilite) formed by accumulation of immiscible sulfide droplets and crystallization from intercumulus liquids. Primary sulfur contents average around 600 ppm, with a mean sulfide d34S value near 0 per mil, similar to the isotopic composition of sulfur in mid-ocean ridge basalt glass. Rocks from a 48-m interval of oxide gabbros have much higher sulfur contents (1090-2530 ppm S) due to the increased solubility of sulfur in Fe-rich melts. Rocks that were locally affected by early dynamothermal metamorphism (e.g., the upper 40 m of the core) have lost sulfur, averaging only 90 ppm S. Samples from the upper 200 m of the core, which underwent subsequent hydrothermal alteration, also lost sulfur and contain an average of 300 ppm S. Monosulfide minerals in some of the latter have elevated d34S values (up to +6.9 per mil), suggesting local incorporation of seawater-derived sulfur. Secondary sulfides (pyrrhotite, chalcopyrite, pentlandite, troilite, and pyrite) are ubiquitous in trace amounts throughout the core, particularly in altered olivine and in green amphibole. Pyrite also locally replaces igneous pyrrhotite. Rocks containing secondary pyrite associated with late low-temperature smectitic alteration have low d34S values for pyrite sulfur (to - 16.6 per mil). These low values are attributed to isotopic fractionation produced during partial oxidation of igneous sulfides by cold seawater. The rocks contain small amounts of soluble sulfate (6% of total S), which is composed of variable proportions of seawater sulfate and oxidized igneous sulfur. The ultimate effect of secondary processes on layer 3 gabbros is a loss of sulfur to hydrothermal fluids, with little or no net change in d34S.

Geochemistry and isotopes at DSDP Site 68-503

Nodules occur in the siliceous calcareous ooze and siliceous marl at Site 503 in the eastern equatorial Pacific. They are present below a depth of about 11 meters throughout the green-colored reduced part of the section down to 228 meters, although they are most abundant between 30 and 85 meters. They are cylindrical or barrel-shaped, up to 70 mm long, and usually have an axial channel through them or are hollow. They appear to have formed around and/or within burrows. XRD studies and microprobe analyses show that they are homogeneous and consist of calcian rhododrosite and minor calcite; Mn is present to the extent of about 30%. Isotopic analyses of the carbonate give carbon values which range from -1.2 per mil to -3.8 per mil, and oxygen isotope compositions vary from +4.0 per mil to +6.0 per mil. These values are different from those for marine-derived carbonates as exemplified by the soft sediment filling of a burrow: d13C, -0.26 per mil; d18O, +1.05 per mil. The carbon isotope data indicate that carbonate derived (possibly indirectly) from seawater was mixed with some produced by organic diagenesis to form the nodules. The d18O values suggest that although they formed near the sediment surface, some modification or the introduction of additional diagenetic carbonate occurred during burial.

Chemical composition of waters, suspended matter, bottom sediments, and benthic organisms along a section from the Ob River estuary (Obskaya Guba) to the central Kara Sea

Biogeochemical behavior of a group of heavy metals and metalloids in water (including their dissolved and suspended particulate forms), bottom sediments, and zoobenthos was studied in the Ob River estuary (Obskaya Guba) - Kara Sea section on the basis of data obtained during Cruise 54 of R/V Akademik Mstislav Keldysh in September-October 2007. Changes in ratios of dissolved and particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and As were shown, as well as growth of adsorbed fractions of the elements in near-bottom suspended matter under mixing of riverine and marine waters. Features of chemical element accumulation in typical benthic organisms of the Obskaya Guba and the Kara Sea were revealed, and their concentrating factors were calculated based on specific conditions of the environment. It was shown that shells of bivalves possessing higher biomass compared to other groups of organisms in the Obskaya Guba play an important role in deposition of heavy metals. In the Obskaya Guba mollusks accumulate Cd and Pb at the background level, whereas Cu and Zn contents appear to be higher than the background level.

Cenozoic terrestrial palynomorphs from the late Oligocene to early Miocene section of sediment core CRP-2/2A (Table 1)

Sparse terrestrial palynomorphs (spores and pollen) were recovered from glacigene Lower Miocene and Oligocene core samples from the Cape Roberts Project (CRP) drillhole CRP-2/2A, Victoria Land Basin, Antarctica. Rarity of palynomorphs probably results from the spares periglacial vegetation in the surrounding landscape at the time of deposition, as well as dilution from rapid sediment accumulation. The Miocene and Late Oligocene vegetation is interpreted as including herb-moss tundra with low-growing woody plants (including Nothofagus and podocarp conifers) in more protected areas, similar to that encountered in the Miocene of CRP-1. Species richness and numbers of specimens increase downhole, a trend that begins very gradually below ~307 mbsf, and increases below ~443 mbsf through the Early Oligocene. These lower assemblages reflect low diversity woody vegetation dominated by several species of Nofhofagus and podocarps, growing in somewhat milder conditions, though still cold temperate to periglacial in the Early Oligocene. The CRP-2/2A core provides new biostratigraphical information, such as the First Appearance Datums (FADS) of Tricolpites sp. a near the Oligocene/Miocene boundary, and Marchantiaceae in the Early/Late Oligocene transition: these are taxa that along with N. lachlaniae, Coptospora spp. and Podocarpidites sp.b characterize assemblages recovered from outcrops of the Pliocene Sirius Group in the Transantarctic Mountains. Some elements of the extremely hardy periglacial tundra vegetation that survived in Antarctica into the Pliocene had their origin in the Oligocene during a time of deteriorating (colder, drier) climatic conditions. The CRP results highlight the long persistence of this tundra vegetation, through approximately 30 million years of dynamically changing climatic conditions. Rare Jurassic and more common Permian-Triassic spores and pollen occur sporadically throughout the core. These are derived from Jurassic Ferrar Group sediments, and from the Permian-Triassic Victoria Group, upper Beacon Supergroup. Higher frequencies of reworked Beacon palynomorphs and coaly organic matter below ~307 mbsf indicate greater erosion of the Beacon Supergroup for this lower part of the core. A color range from black, severely metamorphosed specimens, to light-colored, yellow (indicating low thermal alteration), reworked Permian palynomorphs, indicates local provenance in the dolerite-intruded Beacon strata of the Transantarctic Mountains, as well as areas (now sub-ice) of Beacon strata with little or no associated dolerite well inland (cratonwards) of the present Transantarctic Mountains.

Miocene microflora and palaeoclimatic estimates of the Stetten section (Austria)

Pollen analyses have been proven to possess the possibility to decipher rapid vegetational and climate shifts in Neogene sedimentary records. Herein, a c. 21-kyr-long transgression-regression cycle from the Lower Austrian locality Stetten is analysed in detail to evaluate climatic benchmarks for the early phase of the Middle Miocene Climate Optimum and to estimate the pace of environmental change. Based on the Coexistence Approach, a very clear signal of seasonality can be reconstructed. A warm and wet summer season with c. 204-236 mm precipitation during the wettest month was opposed by a rather dry winter season with precipitation of c. 9-24 mm during the driest month. The mean annual temperature ranged between 15.7 and 20.8 °C, with about 9.6-13.3 °C during the cold season and 24.7-27.9 °C during the warmest month. In contrast, today's climate of this area, with an annual temperature of 9.8 °C and 660 mm rainfall, is characterized by the winter season (mean temperature: -1.4 °C, mean precipitation: 39 mm) and a summer mean temperature of 19.9 °C (mean precipitation: 84 mm). Different modes of environmental shifts shaped the composition of the vegetation. Within few millennia, marshes and salt marshes with abundant Cyperaceae rapidly graded into Taxodiaceae swamps. This quick but gradual process was interrupted by swift marine ingressions which took place on a decadal to centennial scale. The transgression is accompanied by blooms of dinoflagellates and of the green alga Prasinophyta and an increase in Abies and Picea. Afterwards, the retreat of the sea and the progradation of estuarine and wetland settings were a gradual progress again. Despite a clear sedimentological cyclicity, which is related to the 21-kyr precessional forcing, the climate data show little variation. This missing pattern might be due to the buffering of the precessional-related climate signal by the subtropical vegetation. Another explanation could be the method-inherent broad range of climate-parameter estimates that could cover small scale climatic changes.

(Tabls S1) Bulk geochemistry for sediment samples collected from the Cenomanian-Turonian boundary section at Pont d'Issole

Oceanic Anoxic Event 2 (OAE2), spanning the Cenomanian-Turonian boundary (CTB), represents one of the largest perturbations in the global carbon cycle in the last 100 Myr. The d13Ccarb, d13Corg, and d18O chemostratigraphy of a black shale-bearing CTB succession in the Vocontian Basin of France is described and correlated at high resolution to the European CTB reference section at Eastbourne, England, and to successions in Germany, the equatorial and midlatitude proto-North Atlantic, and the U.S. Western Interior Seaway (WIS). Delta13C (offset between d13Ccarb and d13Corg) is shown to be a good pCO2 proxy that is consistent with pCO2 records obtained using biomarker d13C data from Atlantic black shales and leaf stomata data from WIS sections. Boreal chalk d18O records show sea surface temperature (SST) changes that closely follow the Delta13C pCO2 proxy and confirm TEX86 results from deep ocean sites. Rising pCO2 and SST during the Late Cenomanian is attributed to volcanic degassing; pCO2 and SST maxima occurred at the onset of black shale deposition, followed by falling pCO2 and cooling due to carbon sequestration by marine organic productivity and preservation, and increased silicate weathering. A marked pCO2 minimum (~25% fall) occurred with a SST minimum (Plenus Cold Event) showing >4°C of cooling in ~40 kyr. Renewed increases in pCO2, SST, and d13C during latest Cenomanian black shale deposition suggest that a continuing volcanogenic CO2 flux overrode further drawdown effects. Maximum pCO2 and SST followed the end of OAE2, associated with a falling nutrient supply during the Early Turonian eustatic highstand.

Stable and strontium isotope ratios and age determination of ODP Site 130-803

Stratigraphic information from strontium, oxygen, and carbon isotopic ratios has been integrated with diatom and planktonic foraminifer datums to refine the Oligocene to early Miocene chemostratigraphy of Site 803. The Sr isotope results are based on analyses of mixed species of planktonic foraminifer and bulk carbonate samples. 87Sr/86Sr ratios of bulk carbonate samples are, in most cases, less radiogenic than contemporaneous seawater. Estimated sediment ages based on planktonic foraminifer 87Sr/86Sr ratios, using the Sr-isotope-age relation determined by Hess and others in 1989, are in moderately good agreement with the biostratigraphic ages. Chronological resolution is significantly enhanced with the correlation of oxygen and carbon isotope records to those of the standard Oligocene section tied to the Geomagnetic Polarity Time Scale at Site 522. Ages revised by this method and other published ages of planktonic foraminifer datums are used to revise the Oligocene stratigraphy of Site 77 to correlate the stable isotope records of Sites 77 and 803. Comparison of the Cibicidoides stable isotope records of Sites 77 and 574 with paleodepths below 2500 m in the central equatorial Pacific, and Site 803 at about 2000-m paleodepth in the Ontong Java Plateau reveals inversions in the vertical d18O gradient at several times during the Oligocene and in the early Miocene. The shallower water site had significantly-higher d18O values than the deeper water sites after the earliest Oligocene 18O enrichment and before 34.5 Ma, in the late Oligocene from 27.5 to at least 25 Ma, and in the early Miocene from 22.5 to 20.5 Ma. It is not possible to ascertain if the d18O inversion persisted during the Oligocene/Miocene transition because the deeper sites have hiatuses spanning this interval. We interpret this pattern to reflect that waters at about 2000 m depth were cold and may have formed from mixing with colder waters originating in northern or southern high-latitude regions. The deeper water appear to have been warmer and may have been a mixture with warm saline waters from mid- or low-latitude regions. No apparent vertical d13C gradient is present during the Oligocene, suggesting that the age difference of these water masses was small.

Rock magnetic properties and radiocarbon dates of samples obtained on Ile de Possession, South Indian Ocean

A 6200 year old peat sequence, cored in a volcanic crater on the sub-Antarctic Ile de la Possession (Iles Crozet), has been investigated, based on a multi-proxy approach. The methods applied are macrobotanical (mosses, seeds and fruits) and diatom analyses, complemented by geochemical (Rock-Eval6) and rock magnetic measurements. The chronology of the core is based on 5 radiocarbon dates. When combining all the proxy data the following changes could be inferred. From the onset of the peat formation (6200 cal yr BP) until ca. 5550 cal yr BP, biological production was high and climatic conditions must have been relatively warm. At ca. 5550 cal yr BP a shift to low biological production occurred, lasting until ca. 4600 cal yr BP. During this period the organic matter is well preserved, pointing to a cold and/or wet environment. At ca. 4600 cal yr BP, biological production increased again. From ca. 4600 cal yr BP until ca. 4100 cal yr BP a 'hollow and hummock' micro topography developed at the peat surface, resulting in the presence of a mixture of wetter and drier species in the macrobotanical record. After ca. 4100 cal yr BP, the wet species disappear and a generally drier, acidic bog came into existence. A major shift in all the proxy data is observed at ca. 2800 cal yr BP, pointing to wetter and especially windier climatic conditions on the island probably caused by an intensification and/or latitudinal shift of the southern westerly belt. Caused by a stronger wind regime, erosion of the peat surface occurred at that time and a lake was formed in the peat deposits of the crater, which is still present today.

New designs of the ceramic bricks of horizontal hexagonal hollow

This article is intended to state that Technical Drawing is a multiple tool of expression and communication essential to develop inquiry processes, the scientifically basis and comprehension of drawings and technological designs that can be manufactured. We demonstrate graphically and analytically that spatial vision and graphic thinking allow us to identify graphically real life problems, develop proposals of solutions to be analysed from different points of view, plan and develop the project, provide information needed to make decisions on objects and technological processes. From the knowledge of Technical Drawing and CAD tools we have developed graphic analyses to improve and optimize our proposed modification of the geometry of the rectangular cells of conventional bricks by hexagonal cells, which is protected by a Spanish patent owned by the Polytechnic University of Madrid. This new internal geometry of the bricks will improve the efficiency and the acoustic damping of walls built with the ceramic bricks of horizontal hollow, maintaining the same size of the conventional bricks, without increasing costs either in the manufacture and the sale. A single brick will achieve the width equivalent to more than FOUR conventional bricks.

Static and Dynamic Experimental Analysis of the Galloping Stability of Porous H-Section Beams

The phenomenon of self-induced vibrations of prismatic beams in a cross-flow has been studied for decades, but it is still of great interest due to their important effects in many different industrial applications. This paper presents the experimental study developed on a prismatic beam with H-section.The aim of this analysis is to add some additional insight into the behaviour of the flow around this type of bodies, in order to reduce galloping and even to avoid it. The influence of some relevant geometrical parameters that define the H-section on the translational galloping behaviour of these beams has been analysed. Wind loads coefficients have been measured through static wind tunnel tests and the Den Hartog criterion applied to elucidate the influence of geometrical parameters on the galloping properties of the bodies under consideration.These results have been completed with surface pressure distribution measurements and, besides, dynamic tests have been also performed to verify the static criterion. Finally, the morphology of the flow past the tested bodies has been visualised by using smoke visualization techniques. Since the rectangular section beam is a limiting case of the H-section configuration, the results here obtained are compared with the ones published in the literature concerning rectangular configurations; the agreement is satisfactory.

Fire resistance of wooden cellular slabs with rectangular perforations

This paper presents a numerical approach with finite element method in order to predict both the behaviour and the performance of the wooden slabs with rectangular perforations under fire exposure. These typical constructions have good sound absorption, thermal insulation and relevant architectonic features, they are used in many civil engineering applications. These slabs are normally installed at lower level in building constructions essentially due to an easy maintenance requisite. Depending on the installation requirement, the perforated wooden slabs could have an additional insulation material inside the cavities. The proposed numerical model could be applied to different design constructive slab solutions. For this purpose a 3D numerical simulation was conducted with particular attention to the wood thermal properties variation with temperature. The numerical results were compared with those obtained experimentally in laboratory, for two wooden slabs. The fire resistance (performance criteria related to the insulation (I) and integrity (E)) was evaluated, as well as the effect of rectangular perforations into the residual cross section of the slab. This study was conducted in accordance with European Standard EN 1365-2 and using a fire resistance furnace which complies the requirements of EN 1363-1 in the experimental test.