Pore structure and column efficiency of silica monoliths in high performance liquid chromatography (HPLC)

Five different methods were critically examined to characterize the pore structure of the silica monoliths. The mesopore characterization was performed using: a) the classical BJH method of nitrogen sorption data, which showed overestimated values in the mesopore distribution and was improved by using the NLDFT method, b) the ISEC method implementing the PPM and PNM models, which were especially developed for monolithic silicas, that contrary to the particulate supports, demonstrate the two inflection points in the ISEC curve, enabling the calculation of pore connectivity, a measure for the mass transfer kinetics in the mesopore network, c) the mercury porosimetry using a new recommended mercury contact angle values. rnThe results of the characterization of mesopores of monolithic silica columns by the three methods indicated that all methods were useful with respect to the pore size distribution by volume, but only the ISEC method with implemented PPM and PNM models gave the average pore size and distribution based on the number average and the pore connectivity values.rnThe characterization of the flow-through pore was performed by two different methods: a) the mercury porosimetry, which was used not only for average flow-through pore value estimation, but also the assessment of entrapment. It was found that the mass transfer from the flow-through pores to mesopores was not hindered in case of small sized flow-through pores with a narrow distribution, b) the liquid penetration where the average flow-through pore values were obtained via existing equations and improved by the additional methods developed according to Hagen-Poiseuille rules. The result was that not the flow-through pore size influences the column bock pressure, but the surface area to volume ratio of silica skeleton is most decisive. Thus the monolith with lowest ratio values will be the most permeable. rnThe flow-through pore characterization results obtained by mercury porosimetry and liquid permeability were compared with the ones from imaging and image analysis. All named methods enable a reliable characterization of the flow-through pore diameters for the monolithic silica columns, but special care should be taken about the chosen theoretical model.rnThe measured pore characterization parameters were then linked with the mass transfer properties of monolithic silica columns. As indicated by the ISEC results, no restrictions in mass transfer resistance were noticed in mesopores due to their high connectivity. The mercury porosimetry results also gave evidence that no restrictions occur for mass transfer from flow-through pores to mesopores in the small scaled silica monoliths with narrow distribution. rnThe prediction of the optimum regimes of the pore structural parameters for the given target parameters in HPLC separations was performed. It was found that a low mass transfer resistance in the mesopore volume is achieved when the nominal diameter of the number average size distribution of the mesopores is appr. an order of magnitude larger that the molecular radius of the analyte. The effective diffusion coefficient of an analyte molecule in the mesopore volume is strongly dependent on the value of the nominal pore diameter of the number averaged pore size distribution. The mesopore size has to be adapted to the molecular size of the analyte, in particular for peptides and proteins. rnThe study on flow-through pores of silica monoliths demonstrated that the surface to volume of the skeletons ratio and external porosity are decisive for the column efficiency. The latter is independent from the flow-through pore diameter. The flow-through pore characteristics by direct and indirect approaches were assessed and theoretical column efficiency curves were derived. The study showed that next to the surface to volume ratio, the total porosity and its distribution of the flow-through pores and mesopores have a substantial effect on the column plate number, especially as the extent of adsorption increases. The column efficiency is increasing with decreasing flow through pore diameter, decreasing with external porosity, and increasing with total porosity. Though this tendency has a limit due to heterogeneity of the studied monolithic samples. We found that the maximum efficiency of the studied monolithic research columns could be reached at a skeleton diameter of ~ 0.5 µm. Furthermore when the intention is to maximize the column efficiency, more homogeneous monoliths should be prepared.rn

Changes in respiratory mechanics and gas exchange during the acute respiratory distress syndrome

BACKGROUND: The time course of impairment of respiratory mechanics and gas exchange in the acute respiratory distress syndrome (ARDS) remains poorly defined. We assessed the changes in respiratory mechanics and gas exchange during ARDS. We hypothesized that due to the changes in respiratory mechanics over time, ventilatory strategies based on rigid volume or pressure limits might fail to prevent overdistension throughout the disease process. METHODS: Seventeen severe ARDS patients {PaO2/FiO2 10.1 (9.2-14.3) kPa; 76 (69-107) mmHg [median (25th-75th percentiles)] and bilateral infiltrates} were studied during the acute, intermediate, and late stages of ARDS (at 1-3, 4-6 and 7 days after diagnosis). Severity of lung injury, gas exchange, and hemodynamics were assessed. Pressure-volume (PV) curves of the respiratory system were obtained, and upper and lower inflection points (UIP, LIP) and recruitment were estimated. RESULTS: (1) UIP decreased from early to established (intermediate and late) ARDS [30 (28-30) cmH2O, 27 (25-30) cmH2O and 25 (23-28) cmH2O (P=0.014)]; (2) oxygenation improved in survivors and in patients with non-pulmonary etiology in late ARDS, whereas all patients developed hypercapnia from early to established ARDS; and (3) dead-space ventilation and pulmonary shunt were larger in patients with pulmonary etiology during late ARDS. CONCLUSION: We found a decrease in UIP from acute to established ARDS. If applied to our data, the inspiratory pressure limit advocated by the ARDSnet (30 cmH2O) would produce ventilation over the UIP, with a consequent increased risk of overdistension in 12%, 43% and 65% of our patients during the acute, intermediate and late phases of ARDS, respectively. Lung protective strategies based on fixed tidal volume or pressure limits may thus not fully avoid the risk of lung overdistension throughout ARDS.

Mechanisms of perceptual learning of depth discrimination in random dot stereograms.

Perceptual learning is a training induced improvement in performance. Mechanisms underlying the perceptual learning of depth discrimination in dynamic random dot stereograms were examined by assessing stereothresholds as a function of decorrelation. The inflection point of the decorrelation function was defined as the level of decorrelation corresponding to 1.4 times the threshold when decorrelation is 0%. In general, stereothresholds increased with increasing decorrelation. Following training, stereothresholds and standard errors of measurement decreased systematically for all tested decorrelation values. Post training decorrelation functions were reduced by a multiplicative constant (approximately 5), exhibiting changes in stereothresholds without changes in the inflection points. Disparity energy model simulations indicate that a post-training reduction in neuronal noise can sufficiently account for the perceptual learning effects. In two subjects, learning effects were retained over a period of six months, which may have application for training stereo deficient subjects.

Género literario y finalidad discursiva en el DRN

Dentro de la rica tradición histórica de estudios acerca del De rerum natura llama la atención la diversidad de opiniones en cuanto al carácter genérico (principalmente su carácter épico y didáctico) y la finalidad o funcionalidad del poema, puesto que a su vez estos asuntos han sido puntos de inflexión del que se desprenden diversas interpretaciones del texto y aún en nuestros días genera disyuntivas entre los estudiosos. La situación no ha resultado tarea fácil, pues, mientras algunos investigadores declaran a Lucrecio como legislador de la norma didáctica, otros prefieren poner en relieve opiniones diferentes que no apuntan a considerar el poema como una obra de naturaleza didáctica. Así, pues, ante la creciente diversidad de razonamientos que se ha generado en torno a este asunto, consideramos oportuno, tanto a partir de taxonomías genéricas de la antigüedad misma, como de la moderna teoría de los géneros literarios, poner a dialogar algunas de las opiniones más relevantes sobre el particular en busca de aclarar un poco este horizonte, a la vez que agregamos a la discusión que el texto también posee un carácter didáctico en tanto que posee una estructura proléptica

Género literario y finalidad discursiva en el DRN

Dentro de la rica tradición histórica de estudios acerca del De rerum natura llama la atención la diversidad de opiniones en cuanto al carácter genérico (principalmente su carácter épico y didáctico) y la finalidad o funcionalidad del poema, puesto que a su vez estos asuntos han sido puntos de inflexión del que se desprenden diversas interpretaciones del texto y aún en nuestros días genera disyuntivas entre los estudiosos. La situación no ha resultado tarea fácil, pues, mientras algunos investigadores declaran a Lucrecio como legislador de la norma didáctica, otros prefieren poner en relieve opiniones diferentes que no apuntan a considerar el poema como una obra de naturaleza didáctica. Así, pues, ante la creciente diversidad de razonamientos que se ha generado en torno a este asunto, consideramos oportuno, tanto a partir de taxonomías genéricas de la antigüedad misma, como de la moderna teoría de los géneros literarios, poner a dialogar algunas de las opiniones más relevantes sobre el particular en busca de aclarar un poco este horizonte, a la vez que agregamos a la discusión que el texto también posee un carácter didáctico en tanto que posee una estructura proléptica

Género literario y finalidad discursiva en el DRN

Dentro de la rica tradición histórica de estudios acerca del De rerum natura llama la atención la diversidad de opiniones en cuanto al carácter genérico (principalmente su carácter épico y didáctico) y la finalidad o funcionalidad del poema, puesto que a su vez estos asuntos han sido puntos de inflexión del que se desprenden diversas interpretaciones del texto y aún en nuestros días genera disyuntivas entre los estudiosos. La situación no ha resultado tarea fácil, pues, mientras algunos investigadores declaran a Lucrecio como legislador de la norma didáctica, otros prefieren poner en relieve opiniones diferentes que no apuntan a considerar el poema como una obra de naturaleza didáctica. Así, pues, ante la creciente diversidad de razonamientos que se ha generado en torno a este asunto, consideramos oportuno, tanto a partir de taxonomías genéricas de la antigüedad misma, como de la moderna teoría de los géneros literarios, poner a dialogar algunas de las opiniones más relevantes sobre el particular en busca de aclarar un poco este horizonte, a la vez que agregamos a la discusión que el texto también posee un carácter didáctico en tanto que posee una estructura proléptica

Hysteresis phenomena in transverse galloping of triangular cross-section bodies

Transverse galloping is a type of aeroelastic instability characterised by large amplitude, low frequency oscillation of a structure in the direction normal to the mean wind direction. It normally appears in bodies with small stiffness and structural damping, provided the incident flow velocity is high enough. In the simplest approach transverse galloping can be considered as a one-degree-of-freedom oscillator subjected to aerodynamic forces, which in turn can be described by using a quasi-steady description. In this frame it has been demonstrated that hysteresis phenomena in transverse galloping is related to the existence of inflection points in the curve giving the dependence with the angle of attack of the aerodynamic coefficient normal to the incident flow. Aiming at experimentally checking such a relationship between these inflection points and hysteresis, wind tunnel experiments have been conducted. Experiments have been restricted to isosceles triangular cross-section bodies, whose galloping behaviour is well documented. Experimental results show that, according to theoretical predictions, hysteresis takes place at the angles of attack where there are inflection points in the lift coefficient curve, provided that the body is prone to gallop at these angles of attack.

Jovens, políticas públicas e estratégias administrativas: o papel das ideias e dos discursos na constituição do campo e na trajetória das políticas de juventude no Brasil

O objetivo dessa dissertação é analisar como as ideias sobre a juventude, representadas pelos discursos oriundos de diferentes materiais empíricos – documentos governamentais e de organizações da sociedade civil e entrevistas não-estruturadas – e a forma pela qual os jovens são reconhecidos como sujeitos de direitos influenciaram o processo de formação das políticas de juventude no Brasil e institucionalização do tema em âmbito federal, assim como a escolha pelas estratégias administrativas que constituem as principais formas de ação e de gestão governamental no tema. Para isso, adotamos como ponto de partida a reflexão sobre o uso da retórica, por meio de metáforas e narrativas na formação e trajetória das políticas, a existência de coalizões discursivas em seu desenvolvimento e a utilização de frames (enquadramentos interpretativos) no exame dos pontos de inflexão das ações para a juventude no Brasil. Em seguida, identificamos as principais ideias sobre as juventudes presentes no campo e analisamos como elas alimentaram o reconhecimento dos jovens enquanto segmento social diferenciado dos demais em função da sua “condição juvenil” e enquanto sujeitos de direitos integrais. Com base nessas concepções, examinamos a criação e a definição as principais funções da Secretaria Nacional de Juventude, a partir de um debate sobre o conceito de transversalidade, e a formulação e trajetória do Programa Nacional de Inclusão de Jovens (PROJOVEM), adentrando o debate sobre a intersetorialidade nas políticas públicas. A principal contribuição dessa pesquisa foi relacionar como as ideias e discursos influem não apenas na formação de políticas, mas também como as construções sociais que emergem do campo, balizadas pelo reconhecimento dos sujeitos de direitos, também impactam nas estratégias de gestão. Conclui-se, ainda, que apesar da crescente importância atribuída à gestão transversal e à articulação intersetorial na gestão das políticas de juventude no Brasil, são as próprias concepções que orientam sua escolha como estratégias administrativas das quais decorrem os principais limites para a sua operacionalização cotidiana pela administração pública brasileira em nível federal.

Energy profiles for ketene cyclizations. interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products

The energy surface connecting oxazinium olates 9, several possible conformers of ketenes 10 and 11, and the final cyclization products 12, 13 and 14, as well as the isomeric 1,3-oxazine-6-ones 15, ring opening of the latter to N-acylimidoylketenes 16, and subsequent rearrangement of 16 to oxoketenimines 17, azetinones 18, and the cyclization products 19 and 20 are evaluated computationally at the B3LYP/6-31G* and B3LYP/6-311+G*//B3LYP/6-31G* levels. The cyclizations of ketenes to oxazinium olates 9 and oxazines 15 have the characteristics of pseudopericyclic reactions. Plots of the energy vs internal reaction coordinate for the cyclization of transoid acylketenes such as 10 to 9 (via TS1) and 16 to 15 (via TS7) feature two inflection points and indicate that the part of the energy surface above the lower inflection points describe internal rotation of the acyl function in the ketene moiety, and the part below this point describes the cyclization of the cisoid ketene to the planar mesoionic oxazinium olate 9 or oxazinone 15. The 1,3-shifts of the OR group that interconvert ketenes 16 and ketenimines 17 via four-membered cyclic transition states TS8 behave similarly, the first portion (from the ketenimine side) of the activation barrier being due largely to internal rotation of substituents, and the top part being due to the 1,3-shift proper.

Crossing threshold periods in the retail life cycle:Insights from Wal-Mart international

This article takes a broader theoretical perspective of the retail life cycle by incorporating threshold periods at important inflection points in the international growth process. Specifically, it considers one threshold interval between an early phase of disjointed international expansion and a more focused, accelerated international growth programme. It concludes that executives need to consider a set of threshold periods during the development and growth of international store operations, understand why these events occur, and consider in what ways to respond to them to overcome and cross the threshold. Salient lessons are extracted from Wal-Mart's experiences during the threshold period for other international managers. © 2005 Elsevier Ltd. All rights reserved.

Transition in convective flows heated internally

The stability of internally heated convective flows in a vertical channel under the influence of a pressure gradient and in the limit of small Prandtl number is examined numerically. In each of the cases studied the basic flow, which can have two inflection points, loses stability at the critical point identified by the corresponding linear analysis to two-dimensional states in a Hopf bifurcation. These marginal points determine the linear stability curve that identifies the minimum Grashof number (based on the strength of the homogeneous heat source), at which the two-dimensional periodic flow can bifurcate. The range of stability of the finite amplitude secondary flow is determined by its (linear) stability against three-dimensional infinitesimal disturbances. By first examining the behavior of the eigenvalues as functions of the Floquet parameters in the streamwise and spanwise directions we show that the secondary flow loses stability also in a Hopf bifurcation as the Grashof number increases, indicating that the tertiary flow is quasi-periodic. Secondly the Eckhaus marginal stability curve, that bounds the domain of stable transverse vortices towards smaller and larger wavenumbers, but does not cause a transition as the Grashof number increases, is also given for the cases studied in this work.

Transition in plane parallel shear flows heated internally

The stability of internally heated inclined plane parallel shear flows is examined numerically for the case of finite value of the Prandtl number, Pr. The transition in a vertical channel has already been studied for 0≤Pr≤100 with or without the application of an external pressure gradient, where the secondary flow takes the form of travelling waves (TWs) that are spanwise-independent (see works of Nagata and Generalis). In this work, in contrast to work already reported (J. Heat Trans. T. ASME 124 (2002) 635-642), we examine transition where the secondary flow takes the form of longitudinal rolls (LRs), which are independent of the steamwise direction, for Pr=7 and for a specific value of the angle of inclination of the fluid layer without the application of an external pressure gradient. We find possible bifurcation points of the secondary flow by performing a linear stability analysis that determines the neutral curve, where the basic flow, which can have two inflection points, loses stability. The linear stability of the secondary flow against three-dimensional perturbations is also examined numerically for the same value of the angle of inclination by employing Floquet theory. We identify possible bifurcation points for the tertiary flow and show that the bifurcation can be either monotone or oscillatory. © 2003 Académie des sciences. Published by Elsevier SAS. All rights reserved.

Finding line of action of the force exerted on erect spine based on lateral bending test in personalization of scoliotic spine models

In multi-body models of scoliotic spine, personalization of mechanical properties of joints significantly improves reconstruction of the spine shape. In personalization methods based on lateral bending test, simulation of bending positions is an essential step. To simulate, a force is exerted on the spine model in the erect position. The line of action of the force affects the moment of the force about the joints and thus, if not correctly identified, causes over/underestimation of mechanical properties. Therefore, we aimed to identify the line of action, which has got little attention in previous studies. An in-depth analysis was performed on the scoliotic spine movement from the erect to four spine positions in the frontal plane by using pre-operative X-rays of 18 adolescent idiopathic scoliosis (AIS) patients. To study the movement, the spine curvature was considered as a 2D chain of micro-scale motion segments (MMSs) comprising rigid links and 1-degree-of-freedom (DOF) rotary joints. It was found that two MMSs representing the inflection points of the erect spine had almost no rotation (0.0028° ± 0.0021°) in the movement. The small rotation can be justified by weak moment of the force about these MMSs due to very small moment arm. Therefore, in the frontal plane, the line of action of the force to simulate the left/right bending position was defined as the line that passes through these MMSs in the left/right bending position. Through personalization of a 3D spine model for our patients, we demonstrated that our line of action could result in good estimates of the spine shape in the bending positions and other positions not included in the personalization, supporting our proposed line of action.

Critical points in logistic growth curves and treatment comparisons

Several biological phenomena have a behavior over time mathematically characterized by a strong increasing function in the early stages of development, then by a less pronounced growth, sometimes showing stability. The separation between these phases is very important to the researcher, since the maintenance of a less productive phase results in uneconomical activity. In this report we present methods of determining critical points in logistic functions that separate the early stages of growth from the asymptotic phase, with the aim of establishing a stopping critical point in the growth and on this basis determine differences in treatments. The logistic growth model is fitted to experimental data of imbibition of arariba seeds (Centrolobium tomentosum). To determine stopping critical points the following methods were used: i) accelerating growth function, ii) tangent at the inflection point, iii) segmented regression; iv) modified segmented regression; v) non-significant difference; and vi) non-significant difference by simulation. The analysis of variance of the abscissas and ordinates of the breakpoints was performed with the objective of comparing treatments and methods used to determine the critical points. The methods of segmented regression and of the tangent at the inflection point lead to early stopping points, in comparison with other methods, with proportions ordinate/asymptote lower than 0.90. The non-significant difference method by simulation had higher values of abscissas for stopping point, with an average proportion ordinate/asymptote equal to 0.986. An intermediate proportion of 0.908 was observed for the acceleration function method.

Michel Foucault's 'the birth of biopolitics' and contemporary neo-liberalism debates

Neo-liberalism has become one of the boom concepts of our time. From its original reference point as a descriptor of the economics of the ‘Chicago School’ or authors such as Friedrich von Hayek, neo-liberalism has become an all-purpose concept, explanatory device and basis for social critique. This presentation evaluates Michel Foucault’s 1978–79 lectures, published as The Birth of Biopolitics, to consider how he used the term neo-liberalism, and how this equates with its current uses in critical social and cultural theory. It will be argued that Foucault did not understand neo-liberalism as a dominant ideology in these lectures, but rather as marking a point of inflection in the historical evolution of liberal political philosophies of government. It will also be argued that his interpretation of neo-liberalism was more nuanced and more comparative than more recent contributions. The article points towards an attempt to theorize comparative historical models of liberal capitalism.