967 resultados para Center of mass
Resumo:
Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and a-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also. Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly. Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion Ag-2(L-H)(+) where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I) (C).
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The anion radicals CnOn-. (n = 3-6) can be generated by ionization of cyclic carbonyl compounds in the negative ion mode. The ions as well as the corresponding neutral counterparts are probed by means of different mass spectrometric techniques. The results suggest that oxocarbons, i.e. cyclic polyketones, are formed under conservation of the skeletons of the precursor molecules. At least for n = 3, however, the experimental findings indicate partial rearrangement of the expected cyclopropanetrione structure to an oxycarboxylate for the anion, i.e. O-.-C=C-CO2-. For n = 4 and 6 almost complete dissociation of the neutral polyones into carbon monoxide is found, whereas for n = 5 a distinct recovery signal indicates the generation of genuine cyclopentanepentaone.
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Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.
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Hepatocellular carcinoma (HCC) is one of the primary hepatic malignancies and is the third most common cause of cancer related death worldwide. Although a wealth of knowledge has been gained concerning the initiation and progression of HCC over the last half century, efforts to improve our understanding of its pathogenesis at a molecular level are still greatly needed, to enable clinicians to enhance the standards of the current diagnosis and treatment of HCC. In the post-genome era, advanced mass spectrometry driven multi-omics technologies (e.g., profiling of DNA damage adducts, RNA modification profiling, proteomics, and metabolomics) stand at the interface between chemistry and biology, and have yielded valuable outcomes from the study of a diversity of complicated diseases. Particularly, these technologies are being broadly used to dissect various biological aspects of HCC with the purpose of biomarker discovery, interrogating pathogenesis as well as for therapeutic discovery. This proof of knowledge-based critical review aims at exploring the selected applications of those defined omics technologies in the HCC niche with an emphasis on translational applications driven by advanced mass spectrometry, toward the specific clinical use for HCC patients. This approach will enable the biomedical community, through both basic research and the clinical sciences, to enhance the applicability of mass spectrometry-based omics technologies in dissecting the pathogenesis of HCC and could lead to novel therapeutic discoveries for HCC.
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The phase relations have been investigated experimentally at 200 and 500 MPa as a function of water activity for one of the least evolved (Indian Batt Rhyolite) and of a more evolved rhyolite composition (Cougar Point Tuff XV) from the 12·8-8·1 Ma Bruneau-Jarbidge eruptive center of the Yellowstone hotspot. Particular priority was given to accurate determination of the water content of the quenched glasses using infrared spectroscopic techniques. Comparison of the composition of natural and experimentally synthesized phases confirms that high temperatures (>900°C) and extremely low melt water contents (<1·5 wt % H₂O) are required to reproduce the natural mineral assemblages. In melts containing 0·5-1·5 wt % H₂O, the liquidus phase is clinopyroxene (excluding Fe-Ti oxides, which are strongly dependent on fO₂), and the liquidus temperature of the more evolved Cougar Point Tuff sample (BJR; 940-1000°C) is at least 30°C lower than that of the Indian Batt Rhyolite lava sample (IBR2; 970-1030°C). For the composition BJR, the comparison of the compositions of the natural and experimental glasses indicates a pre-eruptive temperature of at least 900°C. The composition of clinopyroxene and pigeonite pairs can be reproduced only for water contents below 1·5 wt % H₂O at 900°C, or lower water contents if the temperature is higher. For the composition IBR2, a minimum temperature of 920°C is necessary to reproduce the main phases at 200 and 500 MPa. At 200 MPa, the pre-eruptive water content of the melt is constrained in the range 0·7-1·3 wt % at 950°C and 0·3-1·0 wt % at 1000°C. At 500 MPa, the pre-eruptive temperatures are slightly higher (by 30-50°C) for the same ranges of water concentration. The experimental results are used to explore possible proxies to constrain the depth of magma storage. The crystallization sequence of tectosilicates is strongly dependent on pressure between 200 and 500 MPa. In addition, the normative Qtz-Ab-Or contents of glasses quenched from melts coexisting with quartz, sanidine and plagioclase depend on pressure and melt water content, assuming that the normative Qtz and Ab/Or content of such melts is mainly dependent on pressure and water activity, respectively. The combination of results from the phase equilibria and from the composition of glasses indicates that the depth of magma storage for the IBR2 and BJR compositions may be in the range 300-400 MPa (13 km) and 200-300 MPa (10 km), respectively.
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The Bruneau–Jarbidge eruptive center of the central Snake River Plain in southern Idaho, USA produced multiple rhyolite lava flows with volumes of <10 km³ to 200 km³ each from ~11.2 to 8.1 Ma, most of which follow its climactic phase of large-volume explosive volcanism, represented by the Cougar Point Tuff, from 12.7 to 10.5 Ma. These lavas represent the waning stages of silicic volcanism at a major eruptive center of the Yellowstone hotspot track. Here we provide pyroxene compositions and thermometry results from several lavas that demonstrate that the demise of the silicic volcanic system was characterized by sustained, high pre-eruptive magma temperatures (mostly ≥950 °C) prior to the onset of exclusively basaltic volcanism at the eruptive center. Pyroxenes display a variety of textures in single samples, including solitary euhedral crystals as well as glomerocrysts, crystal clots and annealed microgranular inclusions of pyroxene ±magnetite± plagioclase. Pigeonite and augite crystals are unzoned, and there are no detectable differences in major and minor element compositions according to textural variety — mineral compositions in the microgranular inclusions and crystal clots are identical to those of phenocrysts in the host lavas. In contrast to members of the preceding Cougar Point Tuff that host polymodal glass and mineral populations, pyroxene compositions in each of the lavas are characterized by single rather than multiple discrete compositional modes. Collectively, the lavas reproduce and extend the range of Fe–Mg pyroxene compositional modes observed in the Cougar Point Tuff to more Mg-rich varieties. The compositionally homogeneous populations of pyroxene in each of the lavas, as well as the lack of core-to-rim zonation in individual crystals suggest that individual eruptions each were fed by compositionally homogeneous magma reservoirs, and similarities with the Cougar Point Tuff suggest consanguinity of such reservoirs to those that supplied the polymodal Cougar Point Tuff. Pyroxene thermometry results obtained using QUILF equilibria yield pre-eruptive magma temperatures of 905 to 980 °C, and individual modes consistently record higher Ca content and higher temperatures than pyroxenes with equivalent Fe–Mg ratios in the preceding Cougar Point Tuff. As is the case with the Cougar Point Tuff, evidence for up-temperature zonation within single crystals that would be consistent with recycling of sub- or near-solidus material from antecedent magma reservoirs by rapid reheating is extremely rare. Also, the absence of intra-crystal zonation, particularly at crystal rims, is not easily reconciled with cannibalization of caldera fill that subsided into pre-eruptive reservoirs. The textural, compositional and thermometric results rather are consistent with minor re-equilibration to higher temperatures of the unerupted crystalline residue from the explosive phase of volcanism, or perhaps with newly generated magmas from source materials very similar to those for the Cougar Point Tuff. Collectively, the data suggest that most of the pyroxene compositional diversity that is represented by the tuffs and lavas was produced early in the history of the eruptive center and that compositions across this range were preserved or duplicated through much of its lifetime. Mineral compositions and thermometry of the multiple lavas suggest that unerupted magmas residual to the explosive phase of volcanism may have been stored at sustained, high temperatures subsequent to the explosive phase of volcanism. If so, such persistent high temperatures and large eruptive magma volumes likewise require an abundant and persistent supply of basalt magmas to the lower and/or mid-crust, consistent with the tectonic setting of a continental hotspot.
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Characterisation of mass transfer properties was achieved in the longitudinal, radial, and tangential directions for four Australian hardwood species: spotted gum, blackbutt, jarrah and messmate. Measurement of mass transfer properties for these species was necessary to complement current vacuum drying modelling research. Water-vapour diffusivity was determined in steady state using a specific vapometer. Permeability values of some species and material directions were extremely low and undetectable by the mass flow meter device. Hence, a custom system based on volume evolution was conceived to determine very low, previously unpublished, wood permeability values. Mass diffusivity and permeability were lowest for spotted gum and highest for messmate. Except for messmate, in the radial direction, the four species measured were less permeable in all directions than the lowest published figures, demonstrating the high impermeability of Australian hardwoods and partly accounting for their relatively slow drying rates. Premeability, water-vapour diffusivity, and associated anisotropic ratio data obtained for messmate were extreme or did not follow typical trends and is consequently the most difficult of the four woods to dry in terms of collapse and checkinng degradation.
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The oxidation rate of a cuprous sulfide pellet suspended in a stream of air was followed by measuring the evolution of SO2 titrimetrically. Thin thermocouples embedded in the center of the sample recorded the variation of temperature during oxidation. The reaction was found to be topochemical and the sample temperature was found to be higher than its surroundings initially for about half an hour. After this initial period, the sample temperature decreased to that of the surroundings and remained constant during the rest of the period of over 5 hr. The apparent activation energy from the experimental data was found to be different for the initial (nonisothermal) and subsequent (isothermal) periods. Rate controlling mechanisms for these two intervals have been proposed based on interface chemical reaction, mass transfer resistance, and heat transfer concepts. Fair agreement is found between the theoretical rates based on transport mechanisms and those obtained experimentally
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This paper presents the results of a computational study of laminar axisymmetric plumes generated by the simultaneous diffusion of thermal energy and chemical species. Species concentrations are assumed small. The plume is treated as a boundary layer. Boussinesq approximations are incorporated and the governing conservation equations of mass, momentum, energy and species are suitably non-dimensionalised. These equations are solved using one time-step-forward explicit finite-difference method. Upwind differencing is employed for convective terms. The results thus obtained are explained in terms of the basic physical mechanisms that govern these flows. They show many interesting aspects of the complex interaction of the two buoyant mechanisms.
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This paper investigates the loss of high mass ions due to their initial thermal energy in ion trap mass analyzers. It provides an analytical expression for estimating the percentage loss of ions of a given mass at a particular temperature, in a trap operating under a predetermined set of conditions. The expression we developed can be used to study the loss of ions due to its initial thermal energy in traps which have nonlinear fields as well as those which have linear fields. The expression for the percentage of ions lost is shown to be a function of the temperature of the ensemble of ions, ion mass and ion escape velocity. An analytical expression for the escape velocity has also been derived in terms of the trapping field, drive frequency and ion mass. Because the trapping field is determined by trap design parameters and operating conditions, it has been possible to study the influence of these parameters on ion loss. The parameters investigated include ion temperature, magnitude of the initial potential applied to the ring electrode (which determines the low mass cut-off), trap size, dimensions of apertures in the endcap electrodes and RF drive frequency. Our studies demonstrate that ion loss due to initial thermal energy increases with increase in mass and that, in the traps investigated, ion escape occurs in the radial direction. Reduction in the loss of high mass ions is favoured by lower ion temperatures, increasing low mass cut-off, increasing trap size, and higher RF drive frequencies. However, dimensions of the apertures in the endcap electrodes do not influence ion loss in the range of aperture sizes considered. (C) 2010 Elsevier B.V. All rights reserved.
Resumo:
Resonant sensors and crystal oscillators for mass detection need to be excited at very high natural frequencies (MHz). Use of such systems to measure mass of biological materials affects the accuracy of mass measurement due to their viscous and/or viscoelastic properties. The measurement limitation of such sensor system is the difficulty in accounting for the ``missing mass'' of the biological specimen in question. A sensor system has been developed in this work, to be operated in the stiffness controlled region at very low frequencies as compared to its fundamental natural frequency. The resulting reduction in the sensitivity due to non-resonant mode of operation of this sensor is compensated by the high resolution of the sensor. The mass of different aged drosophila melanogaster (fruit fly) is measured. The difference in its mass measurement during resonant mode of operation is also presented. That, viscosity effects do not affect the working of this non-resonant mass sensor is clearly established by direct comparison. (C) 2014 AIP Publishing LLC.
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Measured mass flow rates and streamwise pressure distributions of gas flowing through microchannels were reported by many researchers. Assessment of these data is crucial before they are used in the examination of slip models and numerical schemes, and in the design of microchannel elements in various MEMS devices. On the basis of kinetic solutions of the mass flow rates and pressure distributions in microchannel gas flows, the measured data available are properly normalized and then are compared with each other. The 69 normalized data of measured pressure distributions are in excellent agreement, and 67 of them are within 1 +/- 0.05. The normalized data of mass flow-rates ranging between 0.95 and 1 agree well with each other as the inlet Knudsen number Kn (i) < 0.02, but they scatter between 0.85 and 1.15 as Kn (i) > 0.02 with, to some extent, a very interesting bifurcation trend.
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The probability distribution of lift-off velocity of the saltating grains is a bridge to linking microscopic and macroscopic research of aeolian sand transport. The lift-off parameters of saltating grains (i.e., the horizontal and vertical lift-off velocities, resultant lift-off velocity, and lift-off angle) in a wind tunnel are measured by using a Phase Doppler Particle Analyzer (PDPA). The experimental results show that the probability distribution of horizontal lift-off velocity of saltating particles on a bed surface is a normal function, and that of vertical lift-off velocity is an exponential function. The probability distribution of resultant lift-off velocity of saltating grains can be expressed as a log-normal function, and that of lift-off angle complies with an exponential function. A numerical model for the vertical distribution of aeolian mass flux based on the probability distribution of lift-off velocity is established. The simulation gives a sand mass flux distribution which is consistent with the field data of Namikas (Namikas, S.L., 2003. Field measurement and numerical modelling of acolian mass flux distributions on a sandy beach, Sedimentology 50, 303-326). Therefore, these findings are helpful to further understand the probability characteristics of lift-off grains in aeolian sand transport. (c) 2007 Elsevier B.V. All rights reserved.
Resumo:
ENGLISH: Seasonal changes in the climatology, oceanography and fisheries of the Panama Bight are determined mainly by the latitudinal movements of the ITCZ over the region. Evaporation is about 980 mm annually. Rainfall is probably much less than previous estimates because of a discontinuity in the ITCZ. Freshwater runoff from the northern watershed varies from 22 X 109 m3/mo in October-November to 11 X 109 m3/mo in February-March; from the southeastern watershed it varies from 16 X 109 m3/mo in April-June to 9 X 109 m3/mo in October-December. Total annual runoff is about 350 X 109m3. A marked salinity front is found at all seasons off the eastern shore. In the northern part of the Bight temperatures in the upper layers remained fairly constant from May to November; by February the mean temperature had decreased by 4°C and sharp gradients existed in the geographic distributions. Salinities in the upper layers decreased steadily from May to November; by February the mean salinity had increased by 2.5‰. The mean depth of the mixed layer increased from 27 m in May to 40 m in November; by February upwelling decreased it to 18 m. Between November and February upwelling had doubled the amount of P04-P and tripled that of NO3-N in the euphotic zone; surface phytoplankton production and standing crop, and zooplankton concentrations also doubled during this period. Upwelling was about 1.5 m/mo during May-November and about 9.0 m/mo during November-February, the annual total is about 48 m, Mean primary production is about 0.3 gC/m2day during May-December and about 0.6 gC/m2day during January-April; annual production is about 140 gC/m2. A thermal ridge occurred in February running from the northern to the southwestern part of the Bight. Within this ridge was a marked thermal dome coinciding with the center of the cyclonic circulation cell. Upwelling in the dome averaged 16 m/mo in November-February. The fisheries of the Panama Bight annually produce about 30,000 metric tons of food species and about 68,000 m.t. of species used for reduction. Most attempts to further the understanding of tuna ecology were unsuccessful. The apparent abundances of yellowfin and skipjack in the northern part of the Bight appear to be related to the seasonal cycle of upwelling and enrichment, as abundances are greatest in April and May when food appears to be plentiful. The life-cycle of the anchoveta in the Gulf of Panama also appears to be related to upwelling; the species mass varies from about 39,000 m.t. in December to about 169,000 m.t, in April. About 19.1 X 1012 anchoveta eggs are spawned annually. The life-cycles of shrimp in the Panama Bight appear to be related to upwelling as catches are greatest in May-July, about 3-5 months after peak upwelling, and annual catches are inversely correlated with sea level. SPANISH: Los cambios estacionales en la climatología, oceanografía y pesquerías del Panamá Bight están determinados principalmente por el movimiento latitudinal sobre la región de la Zona de Convergencia Intertropical (ZCIT). La evaporación es de unos 980 mm al año. La pluviosidad es probablemente muy inferior a las estimaciones previas a causa de la descontinuidad en la ZCIT. El drenaje de agua dulce, de la vertiente septentrional, varía de 22 x 109m3/mes en octubre-noviembre hasta 11 x 109m3/mes en febreromarzo; el de la vertiente sudeste varía de 16 x 109m3/mes en abril-junio a 9 x 109m3/mes en octubre-diciembre. El drenaje total, anual, es alrededor de 350 x 109m3. En todas las estaciones frente al litoral oriental se encuentra un frente de salinidad marcada. En la parte septentrional del Bight las temperaturas en las capas superiores permanecieron más bien constantes de mayo a noviembre; en febrero la temperatura media había disminuido en unos 4°C y existieron gradientes agudos en las distribuciones geográficas. Las salinidades en las capas superiores disminuyeron constantemente de mayo a noviembre; en febrero la salinidad media había aumentado en 2.5‰. La profundidad media de la capa mixta aumentó de 27 m en mayo a 40 m en noviembre; en febrero el afloramiento disminuyó el espesor de la capa mixta hasta 18 m. Entre noviembre y febrero el afloramiento había duplicado la cantidad de PO4-P y triplicado la de NO3-N en la zona eufótica; la producción superficial de fitoplancton y la biomasa primaria y las concentraciones de zooplancton también se duplicaron durante este período. El afloramiento era cerca de 1.5 mimes durante mayo-noviembre y de unos 9.0 mimes durante noviembre-febrero, el total anual es de unos 48 m. La producción media primaria es aproximadamente de 0.3 gC/m2 al día durante mayo-diciembre y cerca de 0.6 gC/m2 al día durante enero-abril; la producción anual es de unos 140 gC/m2. En febrero apareció una convexidad termal que se extendió de la parte norte a la parte sudoeste del Bight. Dentro de esta convexidad se encontró un domo termal marcado el cual coincidió con el centro de la circulación ciclonal de la célula. El afloramiento en el domo tuvo un promedio de 16 mimes en noviembre-febrero. Las pesquerías del Panamá Bight producen anualmente de cerca 30,000 toneladas métricas de especies alimenticias y unas 68,000 t.m. de especies usadas para la reducción. La mayoría de los esfuerzos realizados con el fin de adquirir más conocimiento sobre la ecología del atún no tuvo éxito. La abundancia aparente del atún aleta amarilla y del barrilete en la parte septentrional del Bight parece estar relacionada con el ciclo estacional del afloramiento y del enriquecimiento, ya que la abundancia mayor en abril y mayo cuando parece que hay abundancia es de alimento. El ciclo de vida de la anchoveta en el Golfo de Panamá parece también que está relacionada al afloramiento. La masa de la especie varía de unas 39,000 t.m. en diciembre a cerca de 169,000 t.m. en abril. Aproximadamente 19.1 x 1012 huevos de anchoveta son desovados anualmente. Los ciclos de vida del camarón en el Panamá Bight parecen estar relacionados con el afloramiento ya que las capturas son superiores en mayo-julio, unos 3-5 meses después del ápice del afloramiento, y las capturas anuales se correlacionan inversamente con el nivel del mar. (PDF contains 340 pages.)
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In this thesis we investigate atomic scale imperfections and fluctuations in the quantum transport properties of novel semiconductor nanostructures. For this purpose, we have developed a numerically efficient supercell model of quantum transport capable of representing potential variations in three dimensions. This flexibility allows us to examine new quantum device structures made possible through state-of-the-art semiconductor fabrication techniques such as molecular beam epitaxy and nanolithography. These structures, with characteristic dimensions on the order of a few nanometers, hold promise for much smaller, faster and more efficient devices than those in present operation, yet they are highly sensitive to structural and compositional variations such as defect impurities, interface roughness and alloy disorder. If these quantum structures are to serve as components of reliable, mass-produced devices, these issues must be addressed.
In Chapter 1 we discuss some of the important issues in resonant tunneling devices and mention some of thier applications. In Chapters 2 and 3, we describe our supercell model of quantum transport and an efficient numerical implementation. In the remaining chapters, we present applications.
In Chapter 4, we examine transport in single and double barrier tunneling structures with neutral impurities. We find that an isolated attractive impurity in a single barrier can produce a transmission resonance whose position and strength are sensitive to the location of the impurity within the barrier. Multiple impurities can lead to a complex resonance structure that fluctuates widely with impurity configuration. In addition, impurity resonances can give rise to negative differential resistance. In Chapter 5, we study interface roughness and alloy disorder in double barrier structures. We find that interface roughness and alloy disorder can shift and broaden the n = 1 transmission resonance and give rise to new resonance peaks, especially in the presence of clusters comparable in size to the electron deBroglie wavelength. In Chapter 6 we examine the effects of interface roughness and impurities on transmission in a quantum dot electron waveguide. We find that variation in the configuration and stoichiometry of the interface roughness leads to substantial fluctuations in the transmission properties. These fluctuations are reduced by an attractive impurity placed near the center of the dot.