Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

Termocronologia (U-Th)He e reativação da margem continental do sudeste do Brasil: seção Serra da Mantiqueira - Gráben da Guanabara

A evolução da margem continental do sudeste do Brasil tem sido discutida por diversos autores desde meados do século passado até os dias atuais, especialmente no contexto da origem e evolução dos escarpamentos e das bacias tafrogênicas. Buscou-se contribuir com novos dados sobre a evolução da área a partir da aplicação da termocronologia de baixa temperatura (U-Th)/He em apatita, que oferece uma sensibilidade significativa para registrar movimentações tectônicas na crosta superior. Foi possível obter idades em 107 cristais de apatita de 18 amostras do embasamento coletadas no perfil com orientação NW-SE, numa seção entre a Serra da Mantiqueira e o Gráben da Guanabara. As idades corrigidas variam entre 250,1 8,7 Ma e 43,5 1,9 Ma (2 σ) e as não corrigidas entre 174,13 3,03 Ma e 27,07 0,60 Ma (1 σ). O Neocretáceo, o Eocretáceo e o Paleoceno são os principais registros no conjunto de dados, em ordem de importância. No Neocretáceo, o intervalo entre 83,6 e 72,1 Ma (Campaniano) representa o maior destaque nos registros termocronológicos, embora os outros registros (Maastrichtiano e Santoniano) também estejam presentes e sejam importantes. As idades do Neocretáceo destacam a importância dos eventos tectonomagmáticos e soerguimento regional na história térmica dessa área, inclusive com idades (~86 Ma) atribuídas ao contexto de soerguimento da Serra do Mar. As idades do Eocretáceo indicam o registro de eventos térmicos mais antigos, vinculados à evolução pré-rifte. Já os dados do Paleoceno estariam associados ao evento de reativação responsável pela implantação do sistema de riftes continentais (~65 Ma) e as idades do Eoceno, restritas à borda de falha da bacia de Resende (49,7 Ma e 43,5 Ma), à reativação do sistema de riftes nessa área. A dispersão de idades foi interpretada como efeito dos danos de radiação já que muitos grãos apresentam correlação entre idade e concentração de urânio (eU). Os padrões de tempo-temperatura (t-T), definidos a partir dos modelos HeFTy calibrados para o modelo de difusão que considera os efeitos de danos de radiação nos cristais, registraram eventos de resfriamento rápido, os quais mostram correlação direta com episódios de reativação e soerguimento na margem continental e com registros nas bacias continentais e marginais. O padrão de aumento das idades com a elevação, assim como da costa em direção ao interior é observado, mas mostra-se alterado pela ocorrência de idades mais jovens associadas à complexa evolução dessa margem continental com desnivelamentos de blocos vinculados à tectônica pós-rift, numa situação que ressalta a influência dos episódios de reativação. As estimativas de denudação total variam entre 1,2 e 2,8 km. As taxas de erosão variam entre 15,2 e 35,3 m/Ma. A evolução da área indica não apenas a influência de um evento específico mas, possivelmente, uma combinação de episódios que se alternaram e/ou atuaram em conjunto em determinados períodos. Os eventos de reativação mais antigos, combinados com os mais recentes, exibem os seus remanescentes na paisagem (serras da Mantiqueira e do Mar e os grábens e bacias sedimentares) e assumem papel fundamental na evolução da área. Os registros de tais episódios podem ser observados nas histórias térmicas das rochas e nos depósitos correlativos nas bacias sedimentares marginais e intracontinentais.

柴达木盆地北缘地区油气成藏过程模拟与含油气系统评价

As an important part of petroleum exploration areas in the west of China, the north part of Qaidam basin is very promising in making great progress for petroleum discovery. But there are still many obstacles to overcome in understanding the process of petroleum formation and evaluation of oil & gas potential because of the complexity of geological evolution in the study area. Based upon the petroleum system theory, the process of petroleum formation is analyzed and the potential of oil & gas is evaluated in different petroleum systems by means of the modeling approach. The geological background for the formation of petroleum systems and the consisting elements of petroleum systems are described in detail. The thickness of strata eroded is estimated by means of vitrinite reflectance modeling, compaction parameter calculating and thickness extrapolating. The buried histories are reconstructed using the transient compaction model, which combines of forward and reverse modeling. The geo-history evolution consists of four stages - sedimentation in different rates with different areas and slow subsidence during Jurassic, uplifting and erosion during Cretaceous, fast subsidence during the early and middle periods of Tertiary, subsidence and uplifting in alternation during the late period of Tertiary and Quaternary. The thermal gradients in the study area are from 2.0 ℃/100m to 2.6 ℃/100m, and the average of heat flow is 50.6 mW/m~2. From the vitrinite reflectance and apatite fission track data, a new approach based up Adaptive Genetic Algorithms for thermal history reconstruction is presented and used to estimate the plaeo-heat flow. The results of modeling show that the heat flow decreased and the basin got cooler from Jurassic to now. Oil generation from kerogens, gas generation from kerogens and gas cracked from oil are modeled by kinetic models. The kinetic parameters are calculated from the data obtained from laboratory experiments. The evolution of source rock maturation is modeled by means of Easy %Ro method. With the reconstruction of geo-histories and thermal histories and hydrocarbon generation, the oil and gas generation intensities for lower and middle Jurassic source rocks in different time are calculated. The results suggest that the source rocks got into maturation during the time of Xiaganchaigou sedimentation. The oil & gas generation centers for lower Jurassic source rocks locate in Yikeyawuru sag, Kunteyi sag and Eboliang area. The centers of generation for middle Jurassic source rocks locate in Saishenteng faulted sag and Yuka faulted sag. With the evidence of bio-markers and isotopes of carbonates, the oil or gas in Lenghusihao, Lenghuwuhao, Nanbaxian and Mahai oilfields is from lower Jurassic source rocks, and the oil or gas in Yuka is from middle Jurassic source rocks. Based up the results of the modeling, the distribution of source rocks and occurrence of oil and gas, there should be two petroleum systems in the study area. The key moments for these two petroleum, J_1-R(!) and J_2-J_3, are at the stages of Xiaganchaigou-Shangyoushashan sedimentation and Xiayoushashan-Shizigou sedimentation. With the kinetic midels for oil generated from kerogen, gas generated from kerogen and oil cracked to gas, the amount of oil and gas generated at different time in the two petroleum systems is calculated. The cumulative amount of oil generated from kerogen, gas generated from kerogen and gas cracked from oil is 409.78 * 10~8t, 360518.40 * 10~8m~3, and 186.50 * 10~8t in J_1-R(!). The amount of oil and gas generated for accumulation is 223.28 * 10~8t and 606692.99 * 10~8m~3 in J_1-R(!). The cumulative amount of oil generated from kerogen, gas generated from kerogen and gas cracked from oil is 29.05 * 10~8t, 23025.29 * 10~8m~3 and 14.42 * 10~8t in J_2-J_3 (!). The amount of oil and gas generated for accumulation is 14.63 * 10~8t and 42055.44 * 10~8m~3 in J_2-J_3 (!). The total oil and gas potential is 9.52 * 10~8t and 1946.25 * 10~8m~3.

中国东海陆架盆地构造-热演化研究

East China Sea Shelf Basin (ECSSB), as a basin with prospect of oil & gas resource and due to its special geological location on the west margin of the west Pacific, attracts a lot of attention from many geologists in the world.Based on systematic temperature measurements, bottom hole temperature (BHT) and the oil temperature data, the geothermal gradients in the ECS SB are calculated and vary from 25 to 43°C/km, with a mean of 32.7°C/km. The geothermal gradient in Fuzhou Sag has the higher value(40.6°C/km) in Taibei Depression than that in others. The lower value (27.2 °C/km) occurs in in Xihu Depression. The middle values occurs in Jiaojiang and Lishui sags in Taibei Depression with a mean value of 34.8 °C/km. Incorporated with the measured thermal conductivity, heat flow values show that the ECSSB is characterized by present-day heat flow around 70.6mW/m2, varying between 55 and 88 mW/m2. No significant difference in heat flow is observed between the Xihu and the Taibei Depressions. These heat flow data suggest that the ECSSB is geothermally not a modem back-arc basin.Applying the paleogeothermal gradient based method, thermal history is reconstructed using vitrinite reflectance (VR) and apatite fission track (AFT) data. The results suggest that the thermal history was different in the Taibei and the Xihu depressions. Paleo-heat flow values when the pre-Tertiary formations experienced their maximum temperature at the end of the Paleocene reached a mean of 81 mW/m2 in the Taibei Depression, much higher than the present-day value. The lower Tertiary sediments in the Xihu Depression experienced maximum temperatures at the end of Oligocene and reached a mean paleo-heat flow value of 83.4 mW/m2. The time, when the paleo-heat flow reached the maximum value, suggests that the ECSSB rifted eastward.Tectonic subsidence analysis shows that the timing of the major rifting episode was different across the ECSSB. The rifting occurred from the Late Cretaceous to the early Eocene in the Taibei Depression, followed by thermal subsidence from the late Eocene to the end of Miocene. In contrast, in the Xihu Depression the initial subsidence lasted until the early Miocene and thermal subsidence to the end of Miocene. From Pliocene to the present, an accelerated subsidence took place all along the West Pacific margin of the east Asia.The thermal lithosphere thickness is determined by temperature profile in the lithosphere, the mantle adiabat or the dry basalt solidus. It indicates that the thermal lithosphere reached the thinnest thickness at the end of Eocene in the Taibei Depression and the end of Oligocene in the Xihu Depression, respectively, corresponding with a value of 57-66km and 56-64km. In Taibei Depression, the lithosphere thickness decreased 16-22km from the end of Mesozoic to Paleocene. After Paleocene, the thickness increased 13-16km and reached 71-79 km at present-day. In Xihu Depression, From the end of Oligocene to present-day, the thickness increased 10-13km and reached 69-76km at present-day. The evolution of the lithosphere thickness is associated closely with the lithosphere stretching.Combining the reconstructed thermal history and the burial history, the maturation of the Jurassic oil-source rock shows that the main hydrocarbon generation phase was in the mid-Jurassic and a secondary hydrocarbon generation occurred at the end of Paleocene. The secondary generation was controlled mainly by the tectono-thermal background during the Paleocene.

句容海安区块热史、成烃史与二次生烃

Jurong -Hai'an block of lower Yangtz area is one of the important petroleum exploration area among the residual marine basins in the south China. In the history of the basin's evolution, the strongly compressing, napping, folding and deforming during Indosinian to Yanshan epoch resulted in destruction of the early formed petroleum pool. Therefore, the strategy exploration of the secondary hydrocarbon generation and later formation of petroleum pool was brought forward for petroleum exploration and planning in the study area..On the basis of tectonic and sedimentary as well as present-day thermal regime evolution, using vitrinite reflectance and apatite fission track data and the paleo-heat flow based method, the basin's thermal history is reconstructed and hence the strata's temperature history are obtained. In addition, the maturation histories of the main four sets of marine hydrocarbon source rocks in the block are calculated. Furthermore, taking the maturity in the end of early Cretaceous as the original maturity and according to the formulas fitted by the secondary hydrocarbon generation model, the secondary hydrocarbon generation potential of the four sets of source rock is evaluated.The results of thermal history reconstruction show that Jurong-Hai'an block was under an uniform thermal setting during the Caledonian to Hercynian period and characterized by middle heat flow (52~57rnW/ m2). The uniform thermal setting was divided during and after Indosinian to Yanshan epoch. Wuwei area of southern Anhui province was under the high heat flow setting(~90 mW/m2)between 236Ma and 137Ma; Jurong area of southern Jiangsu ,Huangqiao area and Subei basin reached its maximum heat flow of 90,84 and 78-82 mW/m2 at 101Ma,157Ma and 56Ma respectivelyThe study of secondary hydrocarbon generation shows that the upper Paleozoic and Triassic source rocks have excellent secondary hydrocarbon generation potential. Silurian source rock posses some secondary hydrocarbon generation. Cambrian source rock, however, nearly has no secondary hydrocarbon generation. Overall there are no advantages of secondary hydrocarbon generation in the southern area of Jiansu. The intensity of secondary hydrocarbon generation in North Jiangsu basin is definitely better than that in the southern area of Jiangsu.

Hydrogen-permeation characteristics of a SrCeO3-based ceramic separation membrane:Thermal, ageing and surface-modification effects

Dense ceramics with mixed protonic-electronic conductivity are of considerable interest for the separation and purification of hydrogen and as electrochemical reactors. In this work, the hydrogen permeability of a Sr_0.97Ce_0.9Yb_0.1O_{3 - δ} (SCYb) membrane with a porous Pt catalytic layer on the hydrogen feed-exposed side has been studied over the temperature range 500-804 °C employing Ar as the permeate sweep gas. A SiO₂-B₂O₃-BaO-MgO-ZnO-based glass-ceramic sealant was successfully employed to seal the membrane to the dual-chamber reactor. After 14 h of exposure to 10% H₂:90% N₂ at 804 °C, the H₂ flux reached a maximum of 33 nmol cm^{- 2} s^{- 1}, over an order of magnitude higher than that obtained on membranes of similar thickness without surface modification. The permeation rate then decreased slowly and moderately on annealing at 804 °C over a further 130 h. Thereafter, the flux was both reproducible and stable on thermal cycling in the range 600-804 °C. The results indicate an important role of superficial activation processes in the flux rate and suggest that hydrogen fluxes can be further optimised in cerate-based perovskites. © 2009 Elsevier B.V. All rights reserved.

Detection of Incipient Thermal Damage Of Carbon Fiber/Epoxy Composites Using Fluorescent Thermal Damage Probes

Thesis (Ph.D.)--University of Washington, 2013

Hepatic concentration of heat shock protein 70 kD (Hsp70) in broilers subjected to different thermal treatments

1. The relationship between repeated thermal treatments and hepatic synthesis of Hsp 70 was studied in broiler chickens.2. Sixty broilers were submitted to 5 different treatments (12 birds each) from day 1 to day 42. Four groups were kept in a thermoneutral environment and subjected to 0, 1, 2 and 3 heat stress episodes at 35 degrees C for 4 h per week (TN-0, TN-1, TN-2 and TN-3, respectively). The last group (HT-35) was reared at a room temperature of 35 degrees C.3. From 39 to 42 old, the birds experienced acute heat stress at 41 degrees C. Resistance to heat stress was evaluated by the time taken for rectal temperature to increase by 3 degrees C above the pre-treatment value. Livers were collected (before and after heat stress) and Hsp70 was determined using Western Blot analysis with monoclonal anti-Hsp70 antibody.4. Resistance to heat stress and concentration of Hsp70 were higher in those birds subjected to more heat stress episodes during the experimental period (TN-3) and HT-35. A positive correlation was observed between Hsp70 concentration and the time taken for a 3 degrees C increase in rectal temperature (r=0.42; P<0.01).5. Exposing birds to episodes of heat stress (35 degrees C) during rearing may improve their resistance to acute heat stress, but the previous thermal history did not seem to influence the hepatocyte Hsp70 content after exposure to more severe heat stress (41 degrees C).

Projected length annealing of etched Sm-152 ion tracks in apatite

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Group analysis method for fission track thermochronology

A methodology to obtain ages and thermal histories of sets of apatite samples from localities with geologically compatible characteristics is described. A methodology exploring the fact that samples with similar geological characteristics should present the same thermal history is proposed. This approach can contribute for the obtainment of more conclusive results by analysing fewer samples than it is necessary when the samples are individually analysed. In order to determine the ages, we use the absolute neutron dosimetry through thin films of natural uranium along with lambda(f) = 8.46 x 10(-17) a(-1). As an example of application of the proposed methodology, we analyse samples collected in a Brazilian region, Sao Francisco Craton, which experienced low tectonic activity. (C) 2008 Elsevier Ltd. All rights reserved.

Consolidation and break-up of the South American platform in southeastern Brazil: Tectonothermal and denudation histories

The different tectonic stages that occurred at the end of the Proterozoic and during the Phanerozoic have an important bearing on the tectonothermal history of the South American Platform and its consolidation. Geochronological data (U/Pb monazite, Ar-40/Ar-39 whole rock) and apatite fission-track analysis, from Precambrian rocks of the southeastern Brazilian coastline, permit the modeling of a long-term thermal history of the crust and constrain variable denudation rates.Using these data, a temperature-time diagram reflects a period of accelerated exhumation during the end of the Brasiliano Orogeny, followed by long stability and reactivation of the platform during the Rifting Phase of the South Atlantic Ocean.U/Pb zircon and monazite (blocking temperature of ca. 650degreesC) data from a series of igneous bodies suggest that a tangential and transpressional tectonic regime occurred between 625 and 610 Ma. During the following escape tectonics, between 610 and 590 Ma the exhumation process indicates cooling rates of ca. 12degreesC/Ma. Ar-40/Ar-39 biotite ages between 540 and 510 Ma (ca. 300degreesC) and a corrected fission-track age on apatites (100degreesC) of 480 Ma indicate an exhumation event related to block tectonics with huge vertical displacement along shear zones.A long stabilization phase, with low exhumation, and cooling rate around 0.25degreesC/Ma was recorded from the Cambro/Ordovician to the Mesozoic. At 65 Ma an acceleration of the exhumation through denudation and reworking of the South American surface with cooling rate of 1.5degreesC/Ma is observed.The uplift of the Mantiqueira and Serra do Mar mountain ranges along the southeast Brazilian coastline works as a climatic barrier provoking lateral erosional processes causing long-term scarp retreat, combined with intense, but progressive denudation towards the continent. A denudation of 2.5 to 4 km was calculated for such processes. This lateral retreat of escarpments and flexural response can provide important insights regarding marginal isostatic uplift and the evolution of offshore sedimentary basins of southeast Brazil.

Thermal treatment effects on phase transitions in P(VDF-TrFE)

Differential scanning calorimetry (DSC) studies were performed for 60/40 P(VDF-TrFE). The results not only confirm the importance of thermal history but also show that the samples with various configurations in terms of ferroelectric phases can be obtained via thermal treatment.

A tectônica meso-cenozóica de parte da borda nordeste da Bacia do Paraná: traços de fissão em apatita

The possible development of thermal events in the central portion of São Paulo state was described based on apatite fission track analysis. Using apatites of sedimentary rocks of the Paraná Basin, modeling the thermal history was made possible due to the homogeneity of the data. Every thermal history begins with a total annealing of fission tracks, related to the Serra Geral magmatism, evolving into a cooling period. In addition to cooling after the magmatism (Early Cretaceous) two other periods of cooling were also detected, registered in the Late Cretaceous/ Paleocene and Eocene, driven as much by uplift with tectonic denudation as by faulting. The nearest portion of the edge of the basin (external to the Dome of Pitanga), registered a period of warming over the Paleocene that can be attributed to the increase in the geothermal gradient. The periods of cooling have a regional and temporal relationship with the tectonic events that occurred in the southeastern Brazil and were described in the crystalline basement. The period of warming, registered in the Late Cretaceous/ Paleocene, has local occurrence and can be found only in the southern portion of the studied area.

Geocronologia por traço de fissão em apatitas de rochas alcalinas: comparação dos diferentes métodos de datação e calibração da dosimetria de nêutrons

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Reconhecimento da tectônica mezozóica-cenozóica na borda leste da Bacia do Paraná através da aplicação de traços de fissão em apatitas no Domo de Pitanga (Sudoeste de Rio Claro, SP)

A tectônica Mesozóica-Cenozóica na borda leste da Bacia do Paraná foi interpretada com base no estudo geocronológico de uma importante feição estrutural conhecida como Domo de Pitanga (sudoeste de Rio Claro, SP), que, como outras estruturas do mesmo tipo presentes na borda da bacia, coincide com grandes alinhamentos estruturais formados pela reativação de estruturas preexistentes no seu embasamento. O método utilizado foi o de datação por análise de traços de fissão em apatitas, o qual permite a modelagem térmica entre 120oC e a temperatura ambiente. Utilizando apatitas de rochas sedimentares, foi possível a modelagem da história térmica da área, graças à homogeneidade dos dados que cada amostra apresentou em função do aquecimento no Eocretáceo pelo magmatismo Serra Geral. Além do resfriamento posterior ao magmatismo marcado pelas idades (Eocretáceo), foram detectadas as principais épocas de resfriamento na área de estudo, sendo elas do Neocretáceo, Paleoceno e, com menor importância, do Mioceno. Estes períodos remontam a importantes eventos tectônicos ocorridos no Sudeste brasileiro, bem descritos no embasamento cristalino. Fica clara a influência desta tectônica de caráter ascensional do embasamento adjacente no interior da bacia, atuando na formação de estruturas, como é o caso do Domo de Pitanga.